Information of defects and 3d electrons in transition metals (Ti, V, Cu) andTiAl-based alloys (Ti 50 Al 50 , Ti 50 Al 48 V 2 , Ti 50 Al 48 Cu 2 ) can be extracted from the positron lifetime and coincidence Doppler broadening spectra. The results show that the 3d electron signals for the transition metals Ti, V and Cu increase with the number of 3d electrons. The 3d electron signal and the electron density for binary TiAl alloy are relatively low due to the (Ti)3d-(Al)3p interactions. The addition of V and Cu atoms to TiAl alloy leads to the increase in the electron densities in bulk and the defects on grain boundaries simultaneously, as well as the enhancement of the 3d electron signal. The 3d electron signal in the spectrum of Ti 50 Al 48 Cu 2 alloy is higher than that of Ti 50 Al 48 V 2 alloy.TiAl alloy, 3d electron, defect, positron annihilation