Mass spectrometric decompositions of complexes of nicotinic acid esters and amides with copper are discussed. Liquid secondary ion mass spectrometry (LSIMS) was used as an ionisation technique and metastable ion spectra were recorded by using B/E linked scans. The fragmentation pathways consist mainly of the loss of one ligand molecule and also the cleavage of amide or ester bonds. It may be possible, on the basis of cleaved neutral fragments, to determine the site of coordination in the gas phase. It was also found that the presence of a chlorine atom affects the fragmentation pathways of complexes.