A series of new 5‐substituted 1H‐tetrazoles bearing bioactive N‐heterocyclic cores were synthesized through [3 + 2] cycloaddition reactions between alkyl nitriles (RCN) and NaN3 in the presence of Cu/aminoclay/reduced graphene oxide nanohybrid (Cu/AC/r‐GO nanohybrid) as a heterogeneous nanocatalyst in water/i‐PrOH (50:50, V/V) media at reflux condition. The influence of factors on a sample reaction including solvent type, temperature, and catalyst amount was discussed. This current protocol has many advantages including inexpensiveness, environmentally benign, broad substrate scope, excellent yields, and easy work‐up procedure. The Cu/AC/r‐GO used in this protocol is a low‐cost catalyst that proved to have considerable chemical and thermal stabilities. This non‐hygroscopic catalyst can be easily recycled, reused, and stored for many consecutive reaction runs without significant loss in its reactivity.