Complexes of lanthanide picrates with bis(pentamethylene)urea (BPMU) with composition Ln(pic)3 · 3(BPMU) (pic = picrate; Ln = La-Er,Y) were synthesized and characterized by CHN analyses, EDTA titrations of lanthanide ions, infrared absorption spectroscopy, X-ray powder patterns, absorption spectra of the Nd and Er compounds and emission spectra of the Sm and Eu compounds. X-ray single-crystal analysis of the Pr compound was carried out and showed that the coordination polyhedron is a distorted monocapped square antiprism with C2v symmetry. This compound presents yellow crystals with symmetry of the monoclinic space group P21/c with a = 12.906(4) Å, b = 21.80(1) Å, c = 22.96(1) Å, β = 105.46(3)°.