Photonanozymes are novel enzyme-mimicking nanomaterials with light-harvesting capacity and have widespread applications in many areas including biosensing, biomedicine, environmental applications, energy, etc. Herein, we introduce freestanding metal-free biocompitable borophene nanosheets (BNSs) exhibiting excellent photoresponsive peroxidase-like activity for biosensing applications. The photo-enhanced peroxidase-like activity of BNSs photonanozyme was indicated to be due to its band gap energy being comparable to the energy of visible light.