Pyrophosphates having P(O)-OP(O) linkages are of interest as biologically active substances. However, only a few research had been focused on POP formation to furnish pyrophosphate. Here, we first developed acetate ion‐assisted POP bond formations using H-Phosphonates as substrates to obtain tetraalkyl pyrophosphates. The reaction mechanism was traced by NMR experiments, revealing that the acetate ion is engaged in the formation of POP bond.