Multiple important physical parameters in the vanadium redox flow battery are difficult to measure accurately, and the multiple important physical parameters (e.g., temperature, flow, voltage, current, pressure, and electrolyte concentration) are correlated with each other; all of them have a critical influence on the performance and life of vanadium redox flow battery. In terms of the feed of fuel to vanadium redox flow battery, the pump conveys electrolytes from the outside to inside for reaction. As the performance of vanadium redox flow battery can be tested only by an external machine—after which, the speed of pump is adjusted to control the flow velocity of electrolyte—the optimum performance cannot be obtained. There is a demand for internal real-time microscopic diagnosis of vanadium redox flow batteries, and this study uses micro-electro-mechanical systems (MEMS) technology to develop a flexible five-in-one (temperature, flow, voltage, current, and pressure) microsensor, which is embedded in vanadium redox flow battery, for real-time sensing. Its advantages include: (1) Small size and the simultaneous measurement of five important physical quantities; (2) elastic measurement position and accurate embedding; and (3) high accuracy, sensitivity, and quick response time. The flexible five-in-one microsensor embedded in the vanadium redox flow battery can instantly monitor the changes in different physical quantities in the vanadium redox flow battery during charging; as such, optimum operating parameters can be found out so that performance and life can be enhancec.