The new compound LaFe4Pl2 was prepared by reaction of LaP and Fe powders with red P in evacuated silica tubes. Single crystals of LaFe4P~2 were obtained by reaction of the elemental components in molten Sn. They are cubic, space group Im3, a = 7.832 A, Z = 2. The structure was determined from single-crystal counter data by Patterson and Fourier methods and refined to R = 0.028 for 193 unique structure factors. It represents a new structural type which can be derived from the CoA% and WAlj2-type structures by filling the (somewhat distorted) icosahedral and octahedral voids with La and Fe atoms respectively. The P atoms are coordinated by two Fe and two P atoms forming a distorted tetrahedron augmented by a La atom outside one face of that tetrahedron. In the polyanionic IFe4Pj2 ]3-framework the P-P bonding distances are somewhat expanded, to accommodate the large La 3÷ cation, which in turn has shorter La-P distances than would be expected from the La-P distances in LaP, LaP 2, and LaP 5. The new compounds LnFe4P~2 (Ln = Ce, Pr, Nd, Sm, Eu), LnRu4P~2 (Ln = La, Ce, Pr, Nd, Eu), and LnOs4P.2 (Ln = La, Ce, Pr, Nd) are isotypic with LaFe4P~2. Their lattice constants indicate valencies IV and II for Ce and Eu, respectively, in the compounds. In CeFe4P~2 the polyanion I FeP 31-is isoelectronic and isostructural with CoP 3.