The reactions of isoxazol-3-amine, thiazol-2-amine, benzo[d]thiazol-2-amine with 4-nitrobenzaldehyde and indole in the absence of a solvent under ball-milling conditions were studied. The reactions proceed through the in situ formation of a Schiff base and subsequent nucleophilic addition of indole at the C=N fragment to form the addition products, α,α-disubstituted azolyl-amines, in yields up to 80%. The structure of the products was proved by physicochemical methods. © 2023, Pleiades Publishing, Ltd.