A key function of battery management system (BMS) is to provide accurate information of the state of charge (SOC) in real time, and this depends directly on the precise model parameterization. In this paper, a novel multi-timescale estimator is proposed to estimate the model parameters and SOC for vanadium redox flow battery (VRB) in real time. The model parameters and OCV are decoupled and estimated independently, effectively avoiding the possibility of cross interference between them. The analysis of model sensitivity, stability, and precision suggests the necessity of adopting different timescales for each estimator independently. Experiments are conducted to assess the performance of the proposed method. Results reveal that the model parameters are online adapted accurately thus the periodical calibration on them can be avoided. The online estimated terminal voltage and SOC are both benchmarked with the reference values. The proposed multi-timescale estimator has the merits of fast convergence, high precision, and good robustness against the initialization uncertainty, aging states, flow rates, and also battery chemistries.