The reaction of [CpCr(CO)3]2 with P4 in toluene at 90 °C for 5 h affords the triple-decker sandwich complex [CpCr(CO)(3-P3)(CpCr)2(,1:5:5-P5)] (1) as a new product, along with the previously described products with P2, P3, and P10 units. The structure of the paramagnetic complex 1 has been established by single-crystal X-ray diffraction methods. A novel complex [{CpCr(CO)2}2(,1:1:2-P2){Mo(CO)4}2{(,1:1:5:5-P5)(CpCr)2}] (2) has been obtained from the reaction of [{CpCr(CO)2}2(,2-P2)] with [Mo(CO)4(NBD)] (NBD = norbornadiene). The X-ray structure of 2 reveals a six-membered Mo2P4 ring combining a Cr2P2 tetrahedral core and a triple-decker sandwich Cr2P5 moiety. The EPR spectra of the paramagnetic (S = 1/2) complexes 1 and 2 are reported. A noticeable hyperfine interaction with two 31P nuclei is observed for 2.