In this work, a Ti2AlNb based intermetallic alloy with the composition of Ti–22Al–24Nb–0.5Mo (at. %) pre-alloyed powder was firstly produced by gas atomization, and then fully dense powder metallurgy (PM) Ti2AlNb alloy was prepared by a hot isostatic pressing (HIPing) procedure. The HIPed alloy shows uniform microstructure with low number of porosities. In order to broaden the application field of PM Ti2AlNb alloys, electron beam welding (EBW) was proposed to join the intermetallics. The joint quality, microstructure and microhardness of PM Ti2AlNb alloy processed by EBW were characterized, and the results showed that the both base alloy and EBW joints have high metallurgy quality.