Andrew Moore, 20, was walking eastbound on U.S. 40 when a Fillmore man driving to work struck him around 5 a.m., Hendricks County Sheriff's Department officials said.
Moore, who was wearing a reflective vest, was pronounced dead at the scene.
Moore, of Concord, Calif., was accompanied by a woman as part of the Crossroads group walking from San Francisco to Washington, D.C. The woman was not injured.
The driver of the car, Terry King, 25, was taken to Hendricks Regional Health with minor injuries.
Hendricks County Sheriff's investigators indicated King was traveling eastbound U.S. 40 when his vehicle struck the pedestrian. Moore was reportedly walking near the median fog line of 40, deputies said.
Police are still investigating the accident but said there was no indication that the vehicle went off the roadway at the time of the crash.
The pedestrians had just been dropped off by a van before the accident.
According to the group's website, young adults walk in shifts each summer on four simultaneous trips from Seattle, San Francisco, San Jose and Los Angeles to Washington, D.C., passing through 40 states.
"They had both just started to pray a rosary a few minutes before he was hit," walk organizer Jim Nolan said in an email. "That's something the group often does while walking."
The Crossroads walks were suspended immediately, Nolan said.