The reaction of LnCl3·7H2O [Ln = La (1), Ce (2)] with salicylic acid (HL) and 1,10-phenanthroline (Phen) at 20 oC in H2O/ethanol gave after work-up and recrystallization two novel lanthanide complexes with general formula [Ln(Phen)2(L)3(HL)]·H2O. Compounds 1 and 2 were characterized by IR and UV-Vis spectroscopy, TGA, CHN as well as by X-ray analysis. According to these results, compounds 1 and 2 are isostructural and contain Ln3+ ions with coordination number nine. Complexes 1 and 2 consist of two Phen, one neutral HL and three L anions (two L anions act as monodentate ligands and the third one is chelating to Ln3+). Thermal decomposition led to primary loss of the Phen molecules. Then HL molecules and finally L moieties left the material to give Ln2O3.