Redox flow battery technology has been increasingly recognized as a promising option for large‐scale grid energy storage. Access to high‐fidelity information on the health status of the electrolyte, including the state‐of‐charge (SOC), is vital to maintaining optimal and economical battery operation. In this study, an ultrasonic probing cell that can be used to measure SOC in real time is designed. This unprecedented, new measurement approach overcomes the influence of varying temperatures by measuring the acoustic attenuation coefficient of the redox flow battery electrolyte online and noninvasively. The new approach is used to estimate the SOC of a vanadium redox flow battery in operando from measured acoustic properties. The accuracy of the SOC estimated from the acoustic properties is validated against SOC calculated by the titration method. The results show that the acoustic attenuation coefficient is a robust parameter for SOC monitoring, with a maximum error of 4.8% and extremely low sensitivity to temperature, while sound speed appears to be less accurate in the benchmark‐inference method, with a maximum error of 22.5% and high sensitivity to temperature. The acoustic measurement approach has great potential for inexpensive real‐time SOC monitoring of redox flow battery operations.