Efficient shielding materials are extremely important to minimize the effect of electromagnetic interference. Currently, various composite materials are being investigated with different shielding efficiencies reported. In this paper, a flexible and free-standing sodium-based chitosan (CH/Na) polymer with copper selenide (CuSe) filler was prepared for electromagnetic shielding. The CH/Na/CuSe polymer matrix was prepared via the direct casting technique at different wt% of CuSe, varying from 2 to 20 wt%. The polymer matrix was then characterised by using Fourier transform infrared (FTIR) spectroscopy to confirm the interaction between the CH/Na and CuSe. The XRD results revealed that the CH/Na/CuSe polymer was successfully formed. Improvement in the electrical conductivity was confirmed by an impedance spectroscopy measurement. The highest electrical conduction recorded was at 3.69 × 10⁻⁵ S/cm for CH/Na/CuSe polymer matrix with 20 wt% CuSe. An increase in total electromagnetic interference (EMI) shielding efficiency (SE_T) of up to 20 dB (99% EM power shield) was achieved, and it can be increased up to 34 dB (99.9% EM power shield) with the thickness of the polymer increased.