A series of phosphorus-substituted germanium(II) complexes, (LGeR)-Ge-1 [L-1 = CH{(CMe)(2,6-(Pr2C6H3N)-Pr-i)}(2); 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph-2; 5b, R = OP(O) ((OBu)-Bu-n)(2); 6a, R = OP(S)Ph-2; 6b, R = OP(S)(OEt)(2)], were synthesized through the direct activation of various organic phosphorus compounds by N-heterocyclic ylide-like germylene 1. These compounds were characterized by IR and NMR spectroscopy, and 4, 5a, 6a, and 6b were further investigated by X-ray crystallography. Interestingly, the reaction of 1 with Ph2P(O)H produced the tricoordinated phosphorus(III) species (LGeOPPh2)-Ge-1 (4) rather than the expected isomeric product (LGeP)-Ge-1(O)Ph-2. The reaction of 1 with dialkylthiophosphoric acid and diphenylthiophosphinic acid resulted in the products 6a and 6b containing the P=S double bond rather than the P=O double bond.