Aluminosilicate spheres with a macroporous core and mesoporous shell (Si/Al ratio of 11) is synthesised by a sol‐gel method utilizing cetyltrimethyl ammonium bromide (CTAB) as a structure directing agent in basic medium. The selective incorporation of aluminium in the silica matrix results in the formation of aluminosilicates with an overall acidity of 0.32 mmol/g with interconnected pores. Direct N‐alkylation reaction is a prototype of C−N bond formation reaction and meso‐ macroporous aluminosilicate is shown to catalyze this reaction with excellent yield. The catalyst is tested and found sustainable for five catalytic cycles even without any high temperature regeneration step.