The syntheses and characterization of three cationic iron-pyrylium complexes (2 +, [2-OMe-3-Fp-5,6-Ph2(C5HO)]+; 3 +, [2-OMe-3-Fp-6-Ph(C5H2O)]+; 4 +, [2-OMe-3-Fp‘-6-Ph (C5H2O)]+) that result from the sequential addition of methyl propiolate and PhC⋮CR (R = Ph, H) to FpBF4 (Fp = η5-C5H5(CO)2Fe) or Fp‘PF6 (Fp‘ = η5-(C5H4Me)(CO)2Fe) are presented. The initially formed cationic Fp-methyl propiolate complex is shown to convert into a complicated mixture that includes the corresponding vinylidene and alkynyl complexes. The iron-pyrylium complexes have been characterized by 1H NMR and IR spectroscopy, elemental analysis, FAB-MS, electrochemical, and fiber-optic-IR and ESR spectroelectrochemical techniques. These metal-pyrylium complexes undergo electron transfer at the pyrylium ring rather than at the metal center. The subsequent chemistry of the neutral species 2 • , 3 • , and 4 • is strongly influenced by the nature of the substituents on the ring. The sterically protected complex 2 + undergoes chemically and electrochemically reversible reductions. The complexes 3 + and 4 + undergo dimerization reactions after reduction presumably through the 4-position of the pyrylium ring.