Steroidal quaternary ammonium compounds 12 and 13 with quaternised nitrogen at positions 3 and 16 of the steroidal nucleus in androstane series were synthesised and their neuromuscular blocking activities and ganglion blocking activities were studied using chick biventer and anaesthetised cat as the models. The bisquaternary compounds 12 and 13 have been found to be greater in potency than D-tubocurarine. Acetoxy derivative 13 has been found to be more potent than pipecuronium bromide taking D-tubocurarine as the standard compound indicating the need of acetoxy function at position 16.