Complex permittivity is one of the most important parameters to characterize the interaction between microwave and medium, especially for microwave-excited plasma. It is convenient to study plasma’s dielectric properties and microwave propagation characteristics by measuring its complex permittivity. A dynamic measurement method of equivalent relative complex permittivity of microwave-excited plasma at atmospheric pressure is proposed in this paper. Firstly, a cavity based on WR-430 at a frequency of 2.45 GHz was specially designed in COMSOL. Then, the samples with different real parts of complex permittivity and loss tangent were simulated in the designed cavity to obtain their corresponding S parameters, and they were used to train the BP neural network until the error was lower than 0.001. A two-port network was built to excite the plasma. The input power, reflected power, and transmitted power could be measured by the transmission reflection method. Finally, the measured power values were converted into S parameters and used as inputs in the BP neural network. The plasma’s real parts of complex permittivity and loss tangent were obtained by inversion. The variation of plasma complex permittivity conforms to the interaction principles between microwave and plasma, which verifies the accuracy of the method.