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Porphyrin nanorods (PNR) were prepared by ionic self-assembly of two oppositely charged porphyrin molecules consisting of free base meso-tetraphenylsulfonate porphyrin (H 4 TPPS 4 2À ) and meso-tetra(N-methyl-4-pyridyl) porphyrin (MTMePyP 4 + M = Sn, Mn, In, Co). ÀMnTMePyP 4 + porphyrin nanorods. The absorption spectra and transmission electron microscopic (TEM) images of these structures were obtained. These porphyrin nanostructures were used to modify a glassy carbon electrode for the electrocatalytic reduction of oxygen, and the oxidation of hydrazine and methanol at low pH. The cyclic voltammogram of PNR-modified GCE in pH 2 buffer solution has five irreversible processes, two distinct reduction processes and three oxidation processes. The porphyrin nanorods modified GCE produce good responses especially towards oxygen reduction at À0.50 V vs. Ag j AgCl (3 M KCl). The process of electrocatalytic oxidation of methanol using PNR-modified GCE begins at 0.71 V vs. Ag j AgCl (