A series of supported highly dispersed CuNi alloy nanocatalysts were fabricated by a coprecipitation method for the N-alkylation of aniline with 2,5-dihydroxymethylfuran under base-free conditions. Various characterizations and catalytic experiments were carried out to systematically investigate the relationship between the catalytic performance and synthetic parameters, such as calcination temperatures, reduction temperatures, and catalyst compositions. The optimized Cu3/17Ni6/17Al8/17O catalysts show good selectivity for the N-alkylation of aniline with 2,5-dihydroxymethylfuran under mild reaction conditions. This work broadens the application of non-noble bimetallic nanocatalysts for N-alkylation reactions and opens new opportunities to synthesize useful HMF derivatives and other valuable biobased chemicals.