Reaction kinetics can be improved by the enhanced electrical contact between different components growing symbiotically. But so far, due to the necessity for material synthesis conditions match, the component structures of cooperative growth are similar, and the materials are of the same type. The collaborative growth of high‐reaction kinetics composite homogeneous core–shell heterostructure between various materials is innovatively proposed with different structures in one step. The NiCo‐LDH and PPy successfully symbiotically grow on activated carbon fiber fabric in one step. The open channel structure of the NiCo‐LDH nanosheets is preserved while PPy effectively wrapped around the NiCo‐LDH. The well‐defined nanostructure with abundant active sites and convenient ion diffusion paths is favorable for electrolyte entry into the entire nanoarrays. In addition, owing to the enhanced electronic interaction between different components through XPS analysis, the NiCo‐LDH@PPy electrode shows outstanding reaction kinetics and structural stability. The as‐synthesized NiCo‐LDH@PPy exhibited excellent super‐capacitive storage capabilities, robust capacitive activity, and good rate survival. Furthermore, an asymmetric supercapacitor (ASC) device made of NiCo‐LDH@PPy and activated carbon (AC) is able to maintain a long cycle life while achieving high power and energy densities.