This paper demonstrates the strategic molecular design of functional polymer monoliths comprised of mesoporous fibers with stimuli‐responsive Joule‐heating properties for the rapid and efficient recovery of viscous fuel oil from water. The mesoporous fibers were composed of carefully selected monomers, which spontaneously entangled with each other to form a spongy monolith in a one‐pot synthesis process. The subsequent addition of polypyrrole nanoparticles to the polymer produced superwettable intertwined fibers with strain‐responsive conductivity, allowing the monolith to be used as a compressible, fibrous, and porous adsorbent with a high‐flux separation capability and a tunable electrical heating effect. This adsorbent was demonstrated to successfully separate different types of low‐viscosity oil from water in a continuous, highly efficient process. It also induced a rapid increase in the temperature during the recovery of marine fuel oil (MFO 380), with a minimal compression of 3% under an external voltage. The proposed adsorbent can thus be used for the effective recovery of various fuel oils and improved further by incorporating other synergistic components for various water‐treatment systems.