Carbon nanotube (CNT) possesses remarkable electrical conductivity, which shows great potential for the application as electromagnetic shielding material. This paper aims to characterize the electromagnetic parameters of a high CNT loading film by using waveguide method. The effects of layer number of CNT laminate, CNT alignment and resin impregnation on the electromagnetic characteristics were analyzed. It is shown that CNT film exhibits anisotropic electromagnetic characteristic. Pristine CNT film shows higher real part of complex permittivity, conductivity and shielding effectiveness when the polarized direction of incident wave is perpendicular to the winding direction of CNT film. For the CNT film laminates, complex permittivity increases with increasing layer number, and correspondingly, shielding effectiveness decreases. The five-layer CNT film shows extraordinary shielding performance with shielding effectiveness ranging from 67 dB to 78 dB in X-band. Stretching process induces the alignment of CNTs. When aligned direction of CNTs is parallel to the electric field, CNT film shows negative permittivity and higher conductivity. Moreover, resin impregnation into CNT film leads to the decrease of conductivity and shielding effectiveness. This research will contribute to the structural design for the application of CNT film as electromagnetic shielding materials.