The development of infrared (IR) surveillance technology has led to a growing interest in thermal camouflage. However, the trade-off relationship between low IR-emissivity and thermal insulation hinders the advance of thermal camouflage materials. Herein, guided by multi-physics simulation, we show a design of asymmetric aramid nanofibers/MXene (ANF/MXene) aerogel film that realizes high-efficient thermal camouflage applications. The rationale is that the asymmetric structure contains a thermal-insulation three-dimensional (3D) network part to prevent effective heat transfer and a low IR-emissivity (~ 0.3) dense surface layer to suppress radiative heat emission. It is remarkable that the synergy mechanism in the topology structure contributes to over 40% reduction of target radiation temperature. Impressively, the tailored asymmetric ANF/MXene aerogel film also enables sound mechanical properties such as a Young’s modulus of 44.4 MPa and a tensile strength of 1.3 MPa, superior to most aerogel materials. It also exhibits great Joule heating performances including low driving voltage (4 V), fast thermal response (< 10 s), and long-term stability, further enabling its versatile thermal camouflage applications. This work offers an innovative design concept to configure multifunctional structures for next-generation thermal management applications.