The Manchester City playmaker suffered fractures to his nose and eye socket after coming off injured in the Champions League final, although he does not require surgery and will aim to be fit for the summer's tournament.
De Bruyne's fellow midfielder Axel Witsel is also in the squad but has already been ruled out of the friendlies with an ongoing Achilles tendon issue, and Martinez is not expected to risk Eden Hazard just yet following another injury-plagued season with Real Madrid.
Thibaut Courtois will be Belgium's undisputed number one at the Euros, but Simon Mignolet could get a run-out for the friendly fixtures, with uncapped goalkeeper Matz Sels - also absent for the majority of the season - taking his place on the bench.
Martinez has plenty of big calls to make in the back three but could settle on Jason Denayer, Toby Alderweireld and Thomas Vermaelen here, while Timothy Castagne ought to start on the right-hand side after starring in that role for Leicester City.
Thorgan Hazard and Yannick Carrasco will battle it out for a spot on the left, and the former may get the nod, while Leicester City's FA Cup hero Youri Tielemans could link up with Hans Vanaken in the middle.
Leandro Trossard should benefit from concerns over Hazard's fitness to start on the left, while Rennes prodigy Jeremy Doku - who already boasts two goals for the national team at the age of 19 - is likely to be given the nod on the right.
Romelu Lukaku will lead the line with aplomb when the Euros rolls around, but a friendly fixture gives Christian Benteke the opportunity to keep the momentum going from his strong second half of the season with Crystal Palace.
Belgium possible starting lineup: Mignolet; Denayer, Alderweireld, Vermaelen; Castagne, Tielemans, Vanaken, T.Hazard; Doku, Benteke, Trossard