DENVER — Colorado joined the National Popular Vote Interstate Compact just four months ago, but the Centennial State may be taking an early off-ramp.

Organizers with Protect Colorado’s Vote announced Wednesday they have collected at least 227,198 signatures to place the National Popular Vote on the November 2020 ballot, easily surpassing the 124,632 valid signatures required to qualify.

“We still have more signatures coming in, too,” said Mesa County Commissioner Rose Pugliese, a Republican, who has helped lead the referendum campaign.

The petitions are due Thursday at the Secretary of State’s office, but if the signatures pass muster, it would mark the first time voters have had an opportunity to decide on a state’s entrance into the National Popular Vote compact, which seeks to render the Electoral College obsolete.

If the National Popular Vote is defeated, it would also represent the first time Colorado voters have repealed an act of the state legislature since 1932, when they overrode a tax hike on oleomargarine.

“I think this NPV repeal has a real shot at passing next year,” said Colorado Republican strategist Dick Wadhams. “It’s going to get on the ballot. In fact, I think it’s going to be a big separation point between Democrats and Republicans, and I’m not sure Democrats are going to enjoy being on that side before it’s over.”

Despite the long odds, organizers say they were stunned by the level of support. The petition campaign began the day after Democratic Gov. Jared Polis signed into law the National Popular Vote, approved by the Democrat-controlled state legislature with no Republican votes.

The measure requires the state’s electors to cast their Electoral College ballots for the presidential candidate who wins the national popular vote, not the candidate with the most state votes, in what supporters hail as a method to make every vote count.

Mr. Polis described the Electoral College as “kind of an antiquated, outdated concept,” according to the Colorado Sun, but there was an outcry from Coloradans who accused the state legislature of attempting to give their votes away to large urban areas like Los Angeles and New York City.

Earlier this month at the Western Conservative Summit in Denver, the Protect Colorado’s Vote booth did brisk business as voters waited in line to sign the referendum petitions.

Monument Mayor Don Wilson, who launched the effort with Ms. Pugliese the day after the bill was signed, said the campaign had received support from voters across the ideological landscape.

“We’re getting a good spectrum of voters,” said Mr. Wilson as voters lined up earlier this month to sign the petitions at the Western Conservative Summit. “We’re seeing more conservatives, but we’re getting commonsense Democrats, and even some progressives.”

Some, but not all. “I did have a 2016 Bernie Sanders delegate tell me, ‘This is wrong,’” he said.

The National Popular Vote campaign launched in 2006, the brainchild of Stanford computer-science professor John R. Koza, and quickly amassed support among Democrats upset by the 2000 presidential election that saw Democrat Al Gore win the popular vote but Republican George W. Bush win the White House.

The campaign bills itself as strictly non-partisan, but so far only blue states have passed the measure. The compact goes into effect when states totaling 270 electoral votes join, a total that now sits at 196 electoral votes after a strong legislative year.

The 2019 legislative session saw a record four blue states — Colorado, Delaware, New Mexico and Oregon — enter into the compact, spurred by the 2016 election, which saw Republican Donald Trump lose the popular vote but win the electoral vote.

One Democrat, Nevada Gov. Steve Sisolak, vetoed it, arguing that the measure would render small-population states like his irrelevant by incentivizing presidential candidates to focus on large urban areas.

In Colorado, the idea of having their vote decided by California, New York and Texas didn’t sit well with many of those who signed the petition.

“What I’ve seen is that people’s votes are very personal to them. They want to make sure they’re protected,” said Ms. Pugliese. “The average person wants their votes to be counted in Colorado.”

Most of the Colorado signatures were gathered by volunteers, although the campaign did hire a canvassing firm “to ensure that we had enough signatures for the ballot,” she said.

The repeal campaign is all but certain to face pushback from Democrats and progressives, an effort that could be led by Mr. Polis, a multi-millionaire who has spent untold millions on liberal candidates and causes as one of the Colorado’s Gang of Four megadonors.

One organization already preparing to fight the referendum is the League of Women Voters of Colorado.

“On the announcement of their signature count, we’re disappointed that partisan politics is driving this effort to undermine voters,” said LWV communications specialist Jessie Koerner. “The League of Women Voters of Colorado is dedicated to ensuring that every voter, regardless of their party identification, makes a powerful difference in who becomes president.”

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