In heterogeneous polymers and emulsions, the volume fraction of the discrete phase and the frequency of electromagnetic waves affect the accuracy of the dielectric model. The integral method was used to modify the Maxwell–Wagner (M–W) heterogeneous dielectric theory, and a new model for the complex dielectric constant of polymers and emulsions was established. The experimental data were compared with the results of the M–W heterogeneous dielectric integral modification model and other theoretical models for different frequencies and volume fractions of the discrete phase. We discovered that with a decreasing volume fraction of the discrete phase, the dominant frequency range of the integral modification model expanded. When the volume fraction of the discrete phase is 10%, the dominant frequency range reaches 3 GHz. When the volume fraction of the discrete phase is 1%, the dominant frequency range reaches 4 GHz. When the volume fraction of the discrete phase is 0.06%, the dominant frequency range of the real part reaches 9.6 GHz, and the dominant frequency range of the imaginary part reaches 7.2 GHz. These results verify the advantages of the M–W modification model, which provides a theoretical basis to study the dielectric properties of polymers and emulsions, as well as for microwave measurement.