Due to the difficulty of absorbing viscous crude oil, there is an urgent need for carbon sponges with excellent photothermal properties and oil‐water separation capabilities to reduce viscosity and facilitate oil absorption. However, the preparation of high‐temperature carbonization leads to poor mechanical properties, low absorption capacity, and stringent preparation conditions. To solve these challenges, a highly hydrophobic flame‐retardant melamine sponge (CPBA@CMS) is designed by assembling sponge at the interface of cobalt–iron Prussian blue (CoFe‐PBA) derived from metal–organic frameworks (MOFs) and conducting low‐temperature catalytic carbonization under nitrogen. The results demonstrate that CPBA@CMS exhibits excellent superhydrophobic properties (water contact angle = 169.7°) and oil absorption capacity (80.7–219.5 g g−1). Furthermore, CPBA@CMS displays remarkable photothermal effects and thermal conductivity, making it adaptable to various environmental conditions. It can rapidly rise to 141 °C under 1 kW m−2 solar irradiation, with the maximum oil absorption rate reaching 98% and the highest oil absorption capacity at 105.5 g g−1. Additionally, CPBA@CMS shows significant fire safety performance, reducing heat release rate by 84.2%, smoke factor by 97.5%, and CO release rate by 81.4%, respectively. It provides an efficient, safe, and sustainable practical solution for effectively addressing spills of crude oil.