The title compounds, Mo(CO)2(Ph2PCH2PPh2)(Ph2PCH2CH2PPh2), Mo(CO)2(dppm)(dppe) 1, and Mo(CO)2(Ph2PCH2CH2PPh2)(Ph2PCH = CHPPh2), Mo(CO)2(dppe)(cis‐vpp) 2, were prepared from Mo(CO)6 and the corresponding bidentate diphosphine ligands in n‐decane under nitrogen atomosphere. Crystals of 1 are monoclinic, space group P 21/c, with a = 19.072(3), b = 11.348(3), c = 23.57(1) Å, β = 99.64(3)°, Z = 4, and the final residual R(F) = 0.044 for 4810 observed reflections; data of 2 are triclinic, space group P 1, with a = 12.091(3), b = 12.186(8), c = 18.934(5) Å, α = 96.93(4),β = 108.15(2), γ = 107.08(4)deg;, Z = 2, and the final residual R(F) = 0.058 for 4570 observed reflections. The distortion of compound 1 is more pronounced than that of compound 2, The two Mo‐P lengths in the same bidentate chelate ligand for both compounds are different. Among them, the two larger Mo‐P bond lengths for compound 2 are similar, but significantly different for 1.