ABSTRACT Burn wounds care and healing are very difficult in clinic. Herein, a multifunctional waterproof hydrogel was fabricated with photothermal antimicrobial and NO anti‐inflammatory properties. In the as‐prepared hydrogel, polyethyleneimine (PEI) and thioctic acid (TA) were cross‐linked by electrostatic interactions and hydrogen bonding while the aggregation of TA could be favor to the formation of hydrophobic caves. Benefit from the caves, CuS and BNN6 (N, N′‐dibutyl‐N, N′‐dinitroso‐1,4‐phenylenediamine) could be incorporated in the PEI/TA‐based hydrogel while the air permeability of the hydrogel could also be increased. Interestingly, the mild increased temperature from the photothermal conversion of CuS not only endowed the as‐prepared hydrogel with photothermal antimicrobial ability but also promoted the release of NO from BNN6. The as‐prepared PEI/TA/CuS/BNN6 hydrogel with good biocompatibility, self‐healing ability and water resistance was suitable for promoting burn wounds healing. It provides a new platform for designing novel wound dressing for burn wounds.