A former Venezuelan beauty queen and her ex-husband were shot dead and their five-year-old daughter wounded after they resisted robbers who attacked their car, police have said.

Monica Spear, 29, and Thomas Berry, 39, were killed on Monday near Puerto Cabello, the country's main port, while on a journey to the capital Caracas, investigators said on Tuesday.

Jose Gregorio Sierralta, the director of the country's investigative police, said their car's tyres had been punctured by "a sharp object placed on the highway". Robbers then moved on the stricken vehicle, and apparently opened fire when the family attempted to lock themselves inside.

Spear, who won Miss Venezuela in 2004 before becoming a soap-opera actress, and Berry, a British citizen, suffered multiple wounds. Their five-year-old daughter, Maya, was shot in the leg, local media reported.

Police in Puerto Cabello arrested five suspects, some under age 18, Sierralta said.

The deaths prompted President Nicolas Maduro to lament on state TV "the loss of a very spiritual young woman" actively involved in various charities.

The opposition leader, Henrique Capriles, called on Maduro to put aside political differences and unite "to win the fight against insecurity" and violent crime that claimed nearly 25,000 lives last year.

Venezuela has one of the world's highest murder rates, ranking 5th globally according to the United Nations.

Spear's death also triggered a wave of anger on social media directed at the populist government's poor record on crime.

She had more than 355,000 followers on Twitter and her feed over the last week included brief videos of holiday scenes.

Spear had acted in numerous soap operas, most recently in Pasion Prohibida' for the US-based Telemundo network.