Precisely regulating the d orbital energy level of the transition metal center in the 2D conductive metal-organic framework (2D cMOF) is critical for determining electrons transfer dynamics and enhancing sensing performances. Herein, this is demonstrated that a 2D cobalt-MOF, decorated with in-plane π conjugated phthalocyanine (Pc), acts as a highly electrically conductive nanofiller in a cellulose-based hydrogel, facilitating the creation of an ultrasensitive self-powered sensing system. The strong conjugation between the π-orbital of Pc and the d-orbital of MOF nanosheets raises the dxy orbital energy level, promoting electrons delocalization. As a result, the optimized 2D MOF@Pc-based conductive hydrogel achieved the highest electrical conductivity of 78 S m−1 due to enhanced electron transfer kinetics. Moreover, as a key component in a triboelectric nanogenerator, supercapacitors, and sensor module, the overall performance of the assembled self-powered sensing micro-system is reinforced, yielding a 75% improvement in sensitivity. The coordination effect between Pc, MOF, and the biopolymers matrix also endowed the hydrogel with outstanding anti-swelling capacity. Additionally, the wearable smart sensor successfully demonstrated its ability to track physiological data and transmit information in underwater. This work presents a progressive strategy for addressing the intrinsic low conductivity of 2D cMOF nanosheets in the sensing field.