The weak interfacial interaction and high sensitivity is a longstanding problem for nitramine explosives. Herein, polyhydroxyethyl acrylate nitrate (PANE) was adopted to passivate three nitramine explosives through a facile and efficient in situ polymerization method. The core-shell structure of the PANE-coated composites was confirmed after detailed morphological and structural characterization. As a result, we find that, the hydrophobic PANE shell improved the adhesion work between the explosives and fluoropolymer (F2314) binder because of the enriched interfacial interactions. Besides, 2% PANE can retard the crystal transformation of CL-20 and HMX explosives by 10.7 °C and 4.3 °C, but does not affect the thermal decomposition behavior. The mechanical sensitivity of PANE-coated composites decreased more significantly than raw explosives and the mixed samples. As a typical example, the impact and friction sensitivity of CL-20@PANE composite with 2.0% shell content is practically halved when compared to raw CL-20 with the characteristicheight (H50) of 32.2 cm and the explosionprobability (P) of 50%. This study offers a simple, effective and universal method for design and preparation of energetic composites with high safety performance.