Besides their positive role, microorganisms are related to a number of undesirable effects, including many diseases, biodeterioration and food spoilage, so when their presence is undesired, they must be controlled. Numerous biocides limiting the development of microorganisms have been proposed, however, in this paper the biocidal and inhibitory activity of quaternary ammonium salts (QASs) and their zwitterionic derivatives is addressed. This paper presents the current state of knowledge about the biocidal activity of QAS and their derivatives. Moreover, the known mechanisms of antimicrobial activity and the problem of emerging resistance to QAS are discussed. The latest trends in the study of surfactants and their potential use are also presented.