The reaction of Ce with the basic polychalcophosphate flux Rb 1 0 P 4 Se 2 5 yielded the quaternary selenophosphate compound Rb 9 Ce(PSe 4 ) 4 . The discrete [Ce(PSe 4 ) 4 ] 9 - anion possesses the highest charge observed in a monometallic complex. The Ce 3 + center is chelated by four bidentate [PSe 4 ] 3 - ligands so it achieves a dodecahedral coordination geometry, and the complex belongs to the dodecahedral sub-class Id (D 2 d -42m), according to the Hoard and Silverton notation. The UV-Vis, optical, IR spectroscopic and magnetism data for the compound are reported.