The use of toxic solvents, high energy consumption, the production of waste and the application of traditional processes that do not follow the principles of green chemistry are problems for the pharmaceutical industry. The organic synthesis of chemical structures that represent the starting point for obtaining active pharmacological compounds, such as benzimidazole derivatives, has become a focal point in chemistry. Benzimidazole derivatives have found very strong applications in medicine. Their synthesis is often based on methods that are not convenient and not very respectful of the environment. A simple montmorillonite K10 (MK10) catalyzed method for the synthesis of benzimidazole derivatives has been developed. The use of MK10 for heterogeneous catalysis provides various advantages: the reaction yields are decidedly high, the work-up procedures of the reaction are easy and suitable, there is an increase in selectivity and the possibility of recycling the catalyst without waste formation is demonstrated. The reactions were carried out in solvent-free conditions and in a short reaction time using inexpensive and environmentally friendly heterogeneous catalysis. It has been shown that the reaction process is applicable in the industrial field.