Two former college volleyball stars and their daughters were killed in a Missouri highway crash while on their way to a tournament.

The head-on collision happened on Friday morning near Lake Saint Louis, Missouri, after a pickup truck crossed over the highway median and struck a minivan, according to the Missouri State Highway Patrol.

Lesley Drury Prather, 44, and Carrie Urton McCaw, 44 — both of Louisville, Kentucky — were travelling to a volleyball tournament in Kansas City with their 12-year-old daughters, Rhyan Prather and Kacey McCaw, on Friday morning when the crash occurred.

Mrs Prather previously played college volleyball for the University of Louisville and Mrs McCaw previously played for Syracuse University in New York. All four people died from the collision.

A Missouri woman named Stephanie Huttegger witnessed the crash and attempted to help with a few other bystanders before paramedics arrived.

“I jumped over the guard rail, jumped across the highway,” Ms Huttegger told Fox 6 Now. “I don’t even know if cars were coming. I just went.”

She added: “As a mom, as a parent, as a human being, it was horrific.”

The first car struck by the truck held two people, both of whom did not suffer any serious injuries. Ms Huttegger said she then discovered the minivan. She pulled out one of the 12-year-old’s from the vehicle with the help of another woman, and they performed CPR for 12 minutes on the child before paramedics arrived.

But the four people in the minivan did not survive.

The pickup driver, identified as Elijah Henderson, suffered non-life threatening injuries from the collision.

An investigation by the St. Charles County prosecutor's office is underway to determine if criminal charges will be brought against Mr Henderson for the collision.

Louisville Volleyball reacted to Mrs Prather’s death on Twitter by sharing an image of the former star with a statement. “We are heartbroken to hear of the passing of Cardinal Forever Lesley Drury Prather (98-01) and her daughter, Rhyan,” the statement read. “Our thoughts are with all of those affected by the fatal crash.”

Louisville Fire Department, which Mrs Prather's worked for as a firefighter, also confirmed the news on its Twitter page. The woman joined the department in 2016.

“This is a terribly sad time for the Louisville Division of Fire and the entire community. Please keep these families and all whose lives have been touched by these four beautiful souls in your thoughts and prayers during this difficult time,” the department wrote.

Syracuse Volleyball released a statement on Saturday about the collision. “The Syracuse Athletics family is deeply saddened by the tragic passing of volleyball alumnae Carrie Urton McCaw ’98, and her daughter, Kacey. Our thoughts are with their families and those affected by the fatal crash during this incredibly difficult time,” the statement read.