Reacting white phosphorus (P4) with sterically encumbered aryl lithium reagents (aryl=2,6‐dimesitylphenyl or 2,4,6‐tBu3C6H2) and B(C6F5)3 gives the unique, isolable Lewis acid stabilized bicyclo1.1.0tetraphosphabutane anion. Subsequent alkylation of the nucleophilic site of the RP4 anion gives access to non‐symmetrical disubstituted bicyclic tetraphosphorus compounds. This novel method enables PC bond formation in a controlled fashion using white phosphorus as starting material. Controlling P4 transformations: Reacting P4 with congested aryl lithium reagents and B(C6F5)3 gives unique, Lewis acid stabilized bicyclo1.1.0tetraphosphabutane anions. Alkylating their nucleophilic site results in a non‐symmetrical disubstituted bicyclic tetraphosphorus compound. This method enables the formation of PC bonds in a controlled fashion using white phosphorus as the starting material.