Poly(ethylene glycol) diacrylate (PEGDA) hydrogel is a very peculiar, fascinating material with good chemical stability and biocompatibility. However, the poor thermal transport phenomenon in PEGDA, limits its performance in cartilage replacement and developing therapies for treating burns. In this article, a combined experimental and atomistic approach was adopted to investigate the thermal transport phenomena in PEGDA hydrogel with different weight concentrations of boron nitride nanoplatelets as a function of water content. The incorporation of boron nitride nanofillers helps in enhancing the thermal conductivity of PEGDA hydrogels, and the reinforcement effect was more dominating at lower water content. Experimental investigation was complemented with molecular dynamics-based studies to capture the effect of defective (bicrystalline) boron nitride nanosheets on the interfacial thermal conductance in PEGDA hydrogels. It can be concluded from the simulations that defective nanosheets are superior reinforcement for enhancing the thermal transport in PEGDA hydrogels, and this is independent of the water content. These biocompatible boron nitride nanoparticle (BNNP)-incorporated PEGDA hydrogels with enhanced thermal conductivity are promising materials in addressing locally overheating tissues such as cartilage replacement. They may have comprehensive utility for biomedical applications such as tissue engineering, drug delivery, biosensors, and burn therapy.