During long-term use, MEMS accelerometers will experience degradation, such as bias and scale factor changes. Bias of MEMS capacitive accelerometers usually comes from the mismatch of parasitic capacitance and sensitive capacitance. This paper focuses on the mismatch of sensitive capacitance and analyzes the mechanism of long-term degradation of MEMS accelerometers. Firstly, the effect of sensitive capacitance mismatch on the performance of a MEMS accelerometer was investigated. Secondly, a method of measuring the mismatch of sensitive capacitance was proposed, and the validation experiment shows that the accuracy of this measurement can be less than 1.10×10−5 of the sensitive capacitance. For the samples in this experiment, the measurement error of this method can be less than 0.36 fF. Finally, a high-temperature acceleration experiment was performed. The mismatch of the sensitive capacitance during the experiment was monitored based on the proposed method, and the experimental results are analyzed. The experimental result demonstrates that the mismatch of sensitive capacitance varies linearly with time. The change rates of sensitive capacitance mismatch for the two samples are 2.95×10−7 C0/h and 2.66×10−7 C0/h in the high-temperature acceleration experiment at 145 °C, respectively. The change in sensitive capacitance mismatch seems small, but it is not to be ignored during long-term use. The rate of change is similar for the same batch of samples. This could imply that the adverse effects due to the mismatch of sensitive capacitance changes can be reduced by compensating for this variation.