The ever-increasing electromagnetic wave (EMW) energy and its reflections may impair human health and information security. An ordinary EMW-absorbing structure usually exhibits limited EMW-reflecting capacity given its ungraded structure in both the micro and macro scales. In this study, four nano-sized graded absorbents are explored by wrapping carbonyl-iron powder with nano-sized silicon dioxide. The micro-scale wrapping effects are assessed via a scanning electron microscopy experiment to identify the best sample, including a 5 wt% coupling agent and a 10 wt% dispersant in CIP ethanol. The 10 mm thick concrete matching layer containing the graded absorbent is built using spraying methodology, and the 15 mm thick absorption layer is fabricated using extruding methodology. The mercury intrusion porosimetry experiments show that the sprayed matching layer incurs maximum porosity at 19.8% while the 3D extruded layer ensures the minimum porosity at 11.13%, strengthening the laminar grading effect to improve the EMW impedance matching. The Naval Research Laboratory experiments corroborate that double-layer structures improve the EMW-reflecting capacity compared to their single-absorption-layer counterparts and that the double-layer element containing the best wrapping effect absorbent yields the best reflection loss value, with a minimum of −14.7 dB and a 9.72 GHz effective bandwidth. The EMW-reflecting mechanism for the novel graded double-layer structure containing the graded nano-sized absorbent is then summarized. Theoretical calculations using the transform line theory suggest that a 15 mm absorbing layer and a 15 mm impedance matching layer is specified as the most optimized configuration, with −10.47 dB in average reflection, −15.18 dB in maximum RL, and 9.56 GHz in effective bandwidth.