Eric Dier and Harry Kane are joined by Tom Carroll (currently on loan at Swansea) and Alex Pritchard (on loan at Brentford) in the squad as the Young Lions bid for a place in next summer's finals in the Czech Republic.
The first leg is at Wolves' Molineux on Friday week, October 10 before the return in Vinkovci on Tuesday, October 14.
It's one of seven play-off matches with all winners joining the hosts in the finals between June 17-30.
Harry, Tom and Alex all featured in the Under-21s last fixtures - Harry on target in both Lithuania and Moldova as England completed their qualifying group unbeaten.
Milos Veljkovic's Serbia take on holders Spain in the play-offs.
The other five play-off ties are as follows - Slovakia v Italy, France v Sweden, Denmark v Iceland, Netherlands v Portugal, Ukraine v Germany.
Meanwhile, Dominic Ball has been called-up for England Under-20s for a tournament in Holland starting next week and Harry Winks is in the England Under-19 squad for the Elite qualifying round of the European U19 Championship in Luxembourg next week. They take on Belarus, Luxembourg and Belgium.
Kyle Walker-Peters made his debut for England Under-18s in a friendly loss against Italy last week.