The d.c. electrical conductivity measurements as a function of temperature of 2,2,2,4,4,4­hexachloro-1,3 bis(2-chlorophenyl)-1,3,2,4-diazadiphosphetidine, (HCCIDP),2,2,2,4,4,4­-hexachloro-1,3-bis(2-bromophenyl)-1,3,2,4-diazadiphosphetidine (HCBrDP), and 2,2,2,4,4,4­-hexachloro-1,3-di-o-tolyl-1),2.4-diazadiphosphetidine (HCMDP) compounds have been carried out. The semiconducting properties of the investigated compounds were arising from electron­ delocalization via intramolecular interaction of p-electrons of (C=C) bonds and electron-donating groups in ortho positions. The conductivity was found to increase in the higher temperature range than in lower due to the trigonal bipyramidal structure which increases the possibility of electron­ delocalization and the interaction of p-electron system.