The ions generated by laser ablation (LA) of calcium and gadolinium oxoborate GdCa4O(BO3)3 (GdCOB) were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS), a powerful tool for the characterization of ionic species produced by laser interaction with solid material. In order to better understand the matter transfer and the mechanism of thin film growth by pulsed-laser deposition (PLD), cationic and anionic clusters generated by UV laser ablation of GdCOB bulk material were studied. Laser ablation of GdCOB leads to the formation of various cluster ions which result from association of CaO, BO and B2O3 building blocks (BB) with different charge carriers (CC): H+, BO+, GdO+ in positive ion mode, and BO, OK−, OH−, Cl−, WO in negative ion mode. LA-FTICRMS investigations allow us to assign a valence state to each metallic atom included in each BB. A +II chemical state may be associated with calcium and +II and +III ones to boron. UV laser ablation of GdCOB therefore induces reduction processes of boron species in the gas phase. The oxygen reactive atmosphere used during PLD experiments allows the growth of stoichiometric thin films by fixation of oxygen on the ablated species. Copyright © 2004 John Wiley & Sons, Ltd.