Copper and manganese complexes containing Schiff bases as ligands, having potential interest in homogeneous catalysis, have been characterised by mass spectrometry using ionspray ionisation. Single stage mass spectrometry allowed us to confirm the molecular weight of complexes in all cases, providing also interesting information about the real form present in solution. Complete structural characterisation of the complexes has been obtained by tandem mass spectrometry, by the analysis of the fragments formed after collisionally induced dissociation of selected precursor ions inside the collision cell of a triple quadrupole mass spectrometer.