<p>Traditional electromagnetic shielding materials primarily enhance reflection and absorption losses by increasing conductivity. While this approach improves shielding effectiveness, it also leads to issues such as impedance mismatch, increased surface reflectivity, and irreversible secondary electromagnetic pollution. Consequently, the development of environmentally friendly electromagnetic interference (EMI) shielding materials with high efficiency and low reflectivity has become a key focus of research. This review examines the critical evaluation criteria and factors that influence the performance and reflectivity of EMI shielding materials. It also highlights recent advances in material tuning mechanisms and structural design strategies for the development of low-reflectivity, sustainable EMI shielding materials. By integrating material and structural design considerations, this review provides a comprehensive overview of strategies for constructing polymer-based low-reflectivity shielding materials, identifies persistent challenges in material design, and discusses future research directions in this field.</p>