The reaction of aniline with methanol was carried out over Zn1-xNixFe2O4 (x=0, 0.2, 0.5, 0.8 and 1) type systems in a fixed-bed down-flow reactor. It was observed that systems possessing low "x" values are highly selective and active for mono N-alkylation of aniline leading to N-methyl aniline. Selectivity for N-methyl aniline over ZnFe2O4 was more than 99% under the optimized reaction conditions. Even at methanol to aniline molar ratio of 2, the yield of N-methyl aniline was nearly 55.5%, whereas its yield exceeded 67% at the molar ratio of 7. The Lewis acid sites of the catalysts are mainly responsible for the good catalytic performance. Cation distribution in the spinel lattice influences their acido-basic properties, and hence, these factors have been considered as helpful to evaluate the activity and stability of the systems.