Cerium(iv) pseudohalide complexes supported by the Kläui tripodal ligand [Co(η5-C5H5){P(O)(OEt)2}3]- (LOEt-) have been synthesized and structurally characterized. The treatment of [CeIV(LOEt)2Cl2] (1) with 2 equivalents of [AgX] in acetonitrile afforded [CeIV(LOEt)2X2] [X- = NCS- (2), N3- (3), F- (4)]. The reaction of 1 with [AgCN] in dichloromethane at -40 °C led to formation of a bimetallic CeIV/AgI cyanide complex that decomposed in solution at room temperature. In the presence of BPh3, 1 reacted with [AgCN] to yield the cyanoborate complex [CeIV(LOEt)2(NCBPh3)2] (6) that is stable in solution. The chlorination of [CeIII(LOEt)2(NO3)] with PhICl2 afforded [CeIV(LOEt)2(NO3)Cl] (7) that reacted with [AgCN] to yield the heterometallic CeIV/AgI cyanide complex [{Ce(LOEt)2(NO3)}2{μ-Ag(CN)2}][AgCl2] (8). The reaction of [CeIV(LOEt)Cl3] with [AgN3] afforded the tetranuclear CeIV oxo azido cluster [Ce4(LOEt)4(μ4-O)(μ2-O)2(μ2-N3)6] (9). The structures of complexes 2, 3, 6 and 9 have been established by X-ray crystallography.