Police in Clinton County said a car crossed the center line and collided with a van just after 4 p.m. Tuesday on Route 220 in Lamar Township.
Authorities said drivers Thomas Zierenberg of Allison Park and Courtney Rebuck of Logantown were pronounced dead at the scene.
Three children—ages 4, 8 and 13—were injured. Their conditions were not released.
The cause of the crash remains under investigation.