AbstractAs an efficient alternative for harnessing the energy from human's biofluid, a wearable energy harvesting–storage hybrid supercapacitor–biofuel cell (SC‐BFC) microfluidic system is established with one multifunctional electrode. The electrode integrates metal–organic framework (MOF) derived carbon nanoarrays with embedded Au, Co nanoparticles on a flexible substrate, and is used for the symmetric supercapacitor as well as the enzyme nanocarriers of the biofuel cell. The electrochemical performance of the proposed electrode is evaluated, and the corresponding working mechanism is studied in depth according to the cyclic voltammetry and density functional theory calculation. The multiplexed microfluidic system is designed to pump and store natural sweat to maintain the continuous biofuel supply in the hybrid SC‐BFC system. The biofuel cell module harvests electricity from lactate in sweat, and the symmetric supercapacitor module accommodates the bioelectricity for subsequent utilization. A numerical model is developed to validate the normal operation in poor and rich sweat under variable situations for the microfluidic system. One single SC‐BFC unit can be self‐charged to ≈0.8 V with superior mechanical durability in on‐body testing, as well as energy and power values of 7.2 mJ and 80.3 µW, respectively. It illustrates the promising scenery of energy harvesting–storage hybrid microfluidic system.