Smart and green construction of noble metal nanostructures on two-dimensional nanomaterials-based flexible paper-like materials have gained extensive attention due to the formed hybrid papers have shown great promise in the applications of energy devices, sensing electronics, actuators, and chemical filters. Herein, a cost-effective and environment-friendly strategy to realize the spontaneous growth of noble metal nanoparticles (Au, Pd, and Pt) on flexible biomimetic MXene paper was proposed. The self-defined regulation of formed noble metal nanoparticles could be easily achieved, and the bimetallic (AuPt, PdPt) nanoparticles decorated MXene paper could be obtained at the mean time. These findings bring a simple, efficient and green way for constructing various hybrid MXene paper with outperforming electrocatalytic activities, which was demonstrated by the sensitive detection of superoxide (O2•−) and the good stability and reproducibility after a long-term usage. The outstanding analytical performance of the obtained AuPtNPs/MXene paper in O2•− monitoring leads to a satisfactory application in real-time extracellular biosensing. The investigation for spontaneous growth and regulation of noble metal nanoparticles on flexible biomimetic MXene paper exhibits a huge application potential for constructing high-performance flexible bioelectronics and energy-related devices.