Synthesis of 9-substituted-8, 9 10, 11-tetrahydro-7H-7, 11-diaza-9k 5 -phosphacycloocta [d,e] naphthalene-9-sulfides/selenides (4-13) was accomplished in three steps. 1,8-diamino naphthalene (2) was reacted with tris (bromomethyl) phosphine (1) in the presence of triethylamine in dry tetrahydrofuran (THF) under N 2 atmosphere to form the corresponding intermediate (3). It was converted to the corresponding sulfide (4) and selenide (5) by the reaction with sulfur and selenium, respectively. The intermediates 4 and 5 were reacted with two achiral alcohols and two achiral amines to obtain the title compounds (6-13). The structures of the title compounds were established by elemental analysis and spectral data (IR, 1 H, 13 C, 31 P NMR, and FAB mass). The antimicrobial activity of these compounds was evaluated and they exhibited significant activity.