Multivariate exponentially weighted moving average (MEWMA) control chart with five different estimators as population covariance matrix is rarely applied to monitor small fluctuations in the statistical process control. In this article, mathematical models of the five estimators (S 1 , S 2 , S 3 , S 4 , S 5 ) are established, with which the relevant MEWMA control charts are obtained, respectively. Thereafter, the process monitoring performance of the five control charts is simulated. And the simulation results show that the S 4 estimator-based MEWMA control chart is of the best performance both in step offset failure mode and ramp offset failure mode. Since the inline process monitoring of photovoltaic manufacturing is intended to be a problem of multivariate statistics process analysis, the feasibility and effectiveness of the proposed model are elaborated in the case study during the cell testing and sorting process control for the fabrication of multicrystalline silicon solar cells.