The O-alkylation of dihydroxo(tetraarylporphyrinato)phosphorus(V) complexes with several kinds of alkyl bromide in MeCN in the presence of K2CO3 and 18-crown-6 ether produced dialkoxo(tetraarylporphyrinato)phosphorus(V) complexes in-moderate-good yields. Similar O-alkylation was applied to dihydroxo(tetraarylporphyrinato)antimony(V) complexes. The O-alkylation proceeded by the occurrence of an SN2 attack of the alkoxide anion of the complexes at the carbon substituted with halides