Trimetaphosphate (TriMP, [P3O9](3-)) reacts with PyAOP ([(H8C4N)(3)PON4C5H3][PF6]) to yield an activated TriMP, [P3O9P(NC4H8)(3)](-) (1), incorporating a phosphonium moiety. Anion 1 is isolated as its bis(triphenylphosphine)iminium (PPN) salt in 70% yield and phosphorylates nucleophiles with elimination of phosphoramide OP(NC4H8)(3). Treatment of 1 with amines (HNRR2)-R-1 generates [(P3O8NRR2)-R-1](2-) (2a: R-1 = R-2 = Et; 2b: R-1 = H, R-2 = Bu-t) in greater than 70% yield as mixed PPN and alkyl ammonium salts. Treatment of 1 with primary alcohols in the presence of a tertiary amine base results in salts of intact TriMP alkyl esters [P3O9R](2-) (3a: R = Me; 3b: R = Et) in greater than 60% isolated yield. Reaction of 1 with [PPN] [H2PO4] provides orthophosphoryl TriMP (4, [P4O12H2](2-)) in 40% yield as the PPN salt. Treatment of 1 with Wittig reagent H2CPPh3 (4 equiv) provides phosphorus ylide [P3O8CHPPh3](2-) (5) in 61% yield as a mixed salt. Ylide 5 reacts with water to provide [P3O8Me](2-) (6) and with aldehydes to give olefins [P3O8CHCHR](2-)(7a: R = H; 7b: R = 4-C6H4Br), products in which one TriMP oxygen is replaced by a phosphonate P-C linkage. Treatment of intact TriMP derivatives 2a, 2b, 3a, and 7a with aqueous tetrabutylammonium hydroxide results in ring opening to linear triphosphate derivatives. X-ray crystal structures are provided for salts of 1, 2a, 3a, and 4.