Carbon‐doped polyaniline (PANI) hydrogels (PFMH) are fabricated by a facile hydrothermal strategy that aniline monomers are in situ polymerized on mesoporous carbons (MC) and carbon fibers (CF) with phytic acids as both cross‐linkers and dopants. Likewise, MC and CF can provide heterogeneous active sites to initiate the polymerization, acting as the skeletons within multi‐dimensional interconnected channel structures. First‐principles density functional theory calculations show that the interactions between different bases of PANI and MC/CF are all adsorptive prone to possess the separation‐free structure, but the adsorptive interactions between different bases and MC are significantly stronger than those of CF. Therefore, MC would be tightly anchored by PANI chains to improve the mechanical strength, while CF can provide favorable conductivity interconnected network skeletons. As such, the electrical conductivity and fracture strength of PFMH are measured high up to 13.32 S m−1 and 233.4 kPa at the fracture deformation (54.7%), respectively. PFMH as supercapacitor (SC) electrodes can achieve the gravimetric specific capacitance of 637.9 F g−1 at 1 A g−1. In particular, the as‐fabricated flexible all‐solid‐state SCs can maintain normal operation under various deformation conditions, showing the great potential to become an advanced power device for wearable electronics.