Abstract The synthesis of amides belongs to traditional experimental tasks not only in organic chemistry exercises at universities but also at chemically focused secondary schools or in special practices at general high schools. An example of such a synthesis may be the preparation of acetanilide via reaction of aniline with acetic acid or acetic anhydride. However, both of these reactions are associated with a rather long reaction time and certain hazards that limit their straightforward use in pedagogical practice. Conveniently, the reaction of aniline with acetic acid may be significantly optimised if it is performed under solvent-free conditions in the presence of microwaves, which reduces considerably the reaction time and provides very good yield, compared to traditional heating by a heating nest. In this study, the main pedagogical aim of the experimental design is elucidation of the influence of the structure of the amines on the course of the reaction with formic acid through inquiry-based learning. Specifically, the proposed experiments consist in investigation of the chemical yield achieved in microwave assisted reactions of aniline and its derivatives with formic acid in such a way that is adequate for constructive learning of undergraduate chemistry students. The selected series of amines involves aniline, 4-methoxyaniline, 4-chloroaniline, and 4-nitroaniline. In accordance with the chemical reactivity principles, students gradually realise that the influence of the substituent is reflected in the reaction yield, which grows in the following order: N-(4-nitrophenyl)formamide ˂ N-(4-chlorophenyl)formamide ˂ N-phenylformamide ˂ N-(4-methoxyphenyl)formamide. Therefore, the results of the experiments enable students to discover that stronger basicity of the amine increases the yield of the amide. In order to deepen the students’ chemical knowledge and skills, the concept of the experiments was transformed to support inquiry-based student learning. The proposed experiments are intended for experimental learning in universities educating future chemistry teachers, but they may be also utilised in the form of workshops for students at secondary schools of a general educational nature.