Crosslinking polymers to form networks is a universal and routinely applied strategy to improve their stability and endow them with solvent resistance, adhesion properties, etc. However, the chemical crosslinking of common commercial polymers, especially for those without functional groups, cannot be achieved readily. In this study, we utilized low-molecular weight poly(glycidyl azide) (GAP) as polymeric crosslinkers to crosslink various commercial polymers via simple ultraviolet light irradiation. The azide groups were shown to decompose upon photo-irradiation and be converted to highly reactive nitrene species, which are able to insert into carbon-hydrogen bonds and thus crosslink the polymeric matrices. This strategy was demonstrated successfully in several commercial polymers. In particular, it was found that the crosslinking is highly localized, which could endow the polymeric matrices with a decent degree of crosslinking without significantly influencing other properties, suggesting a novel and robust method to crosslink polymeric materials.