The aim of the study was to determine the relation between the biological activity of two homologous series of cationic gemini surfactants, which are quaternary ammonium salts, and their structure. The measure of the biological activity of the compounds was assumed to be the effects they exert on the membrane of erythrocytes, treated as a simple model of the biological membrane. In particular, it was determined the effects of the compounds on hemolysis and the osmotic resistance of erythrocytes and the fluidity of erythrocyte membrane, and the packing arrangement of the polar heads of membrane lipids. The results have shown that surfactants affect the osmotic resistance of erythrocytes to various degrees, and at sufficiently high concentrations operate destructively on their membrane, eventually causing hemolysis, modify the fluidity of erythrocyte membrane and affect the arrangement of polar heads of membrane lipids. Additionally, the results showed that that activity depends on a surfactant's chemical structure, in particular, on the length of its alkyl chain and structure of the polar head group that determines the spacing between the chains. In both used new series the compounds containing 10, 12 and 14 carbon atoms in a chain possess a high biological activity. In addition, the surfactants with larger spaces between the chains are more active than those with smaller spacing. The investigations have revealed a high activity of compounds with longer chains and bigger polar heads. The results of the study may find application when designing a molecular structure and synthesizing new compounds of specific, desired activity.