The 41-year-old Schilling, currently on the 60-day disabled list with a right biceps/shoulder injury, will play catch with assistant trainer and rehab coordinator Mike Reinold. He will make 25 throws from 60 feet.
"It doesn't sound like a lot, but it's a big day for him," Red Sox manager Terry Francona said. "His last month has been pretty good. ... He's got himself to the point where Mike's excited about letting him do this. We're all excited. This is a nice step. He's excited, and he should be."
Assuming all goes well with Tuesday's session, the Red Sox will place Schilling on a throwing program beginning later this week, thought to include more side throwing sessions and eventually bullpen work.
There is no timetable set for Schilling's return, but the right-hander has said he plans on returning to the Boston rotation sometime this season.
After being shut down in January due to immense pain in the shoulder, Schilling has been undergoing a strength and conditioning program with Reinold since receiving a cortisone shot in February.
Schilling said last Friday he hoped to start throwing in the next 10 days, but he has shown the team training staff enough progress to begin earlier.
Scott McNeish is an associate reporter for MLB.com. This story was not subject to the approval of Major League Baseball or its clubs.