Polymer modification can improve the stability and corrosion resistance of wood, but it could create defects inside wood during the modification processing. Detection of defects inside polymer-modified wood can reduce wood losses and prevent the occurring of defects. Data simulation and tomographic imaging of polymer-modified wood internal defects were carried out using electromagnetic waves with nondestructive testing. This study constructed the polymer-modified wood models, simulated the electromagnetic scattering wave, and used the total focusing method to perform tomography of the defects in the polymer-modified wood. By analyzing the imaging characteristics of different types of defects, the effectiveness of electromagnetic waves in the detection of internal defects of polymer-modified wood was proved. This method can be extended to test internal defects of other high molecular polymers.