Dependence on psychoactive substances has always been present in social communities, therefore, even in the modern era, new methods of overcoming it must be constantly found. Psychoactive substances are most simply divided into alcohol, cigarettes and drugs, and addiction to them can be psychological, physical or combined. The causes of the development of addiction in an individual are usually of genetic origin, although it is also influenced by the need for social approval, curiosity, facing certain life difficulties and the presence of a particular mental disorder. In social work with addicts, numerous methods are mentioned, among which one of the most effective is group work, which implies a homogeneous group of people interacting together and with common interests. Although the beginnings of group work date back to the period before Christ, this method of social work was officially developed only in the 19th and 20th centuries. In order to successfully overcome their addiction, the participants of the group process (including its leader) should adhere to certain organizational and ethical principles. Furthermore, in group work with addicts, expert teams and competent bodies play a big role, which should know how to implement it in appropriate ways. On the other hand, the role of therapeutic communities, workshops and other sociotherapeutic forms of group work with addicts is manifested in the fact that their participants get the opportunity for personal growth in community, mutual support and education, which can greatly help them in successfully overcoming addiction. However, it is necessary for social workers to cooperate with other competent authorities such as health and educational institutions, as well as to conduct various researches on the mentioned topic in order to see the true value and importance of group processes in social work with addicts. The aim of the paper is therefore to show the role and inevitable importance of the application of group work in social work with people addicted to psychoactive substances, as well as its main advantages, but also disadvantages, challenges and future potential of its active use in the mentioned profession. Also, as a subject of research, the paper touches on the definition of psychoactive substances on a general level and their impact on the mental health and overall lifestyle of their addicts, with the primary purpose being to emphasize their harmfulness, but also the ways of prevention, protection and preservation from them. Since this is an extremely sensitive group of people, i.e. addicts of the mentioned substances, the paper shows how important it is to apply group work in cooperation with them as one of the most important methods of achieving social work.