Novel N-amino benzylthiolates were synthesized via multicomponent reaction of malononitrile, isothiocyanates and benzyl halides under conventional and solvent-free conditions. Various electron-donating and -withdrawing substitutes within both isothiocyanates and benzyl halides were used to demonstrate the efficiency of new methodology. A broad spectrum of antibacterial and antifungal activities were observed especially within benzyl halides containing electron-withdrawing aryl substituents.