The past decade has witnessed the advances of infrared (IR) thermal camouflage materials, but challenges remain in breaking the trade-off nature between emissivity and mechanical properties. In response, we identify the key role of a moderate reprotonation rate in the aramid nanofiber (ANF)/MXene film toward a surface-to-bulk alignment. Theoretical simulation demonstrates that the ordered ANF/MXene surface eliminates the local high electric field by field confinement and localization, responsible for the low IR emissivity. By scrutinizing the surface/interface chemistry, the processing optimization is achieved to develop an ordered and densely stacked ANF/MXene film, which features a low emissivity of 16%, accounting for sound IR thermal camouflage performances including a wide camouflage temperature range of 50-200 °C, a large reduction in radiation temperature from 200.5 to 63.6 °C, and long-term stability. This design also enables good mechanical performance such as a tensile strength of 190.8 MPa, a toughness of 12.1 MJ m-3, and a modulus of 7.9 GPa, responsible for better thermal camouflage applications. The tailor-made ANF/MXene film further attains an electromagnetic interference (EMI) shielding effectiveness (40.4 dB) in the X-band, manifesting its promise for IR stealth compatible EMI shielding applications. This work will shed light on the dynamic topology reconstruction of camouflage materials for boosting thermal management technology.