The rational design and fabrication of promising electrodes with prominent energy storage property and conversion performance is crucial for supercapacitors and electrocatalysis. Herein, potato-chip-like Co-Ni layered double hydroxide@polypyrrole-cotton pads (CoNi-LDH@PCPs) composite was synthesized by in situ polymerization, which was coupled with facile solution reaction and ion-exchange etching process. An interesting potato-chip-like structure can effectively expedite the kinetics of the electrode reactions, while the three-dimensional PCPs texture affords efficient pathways for charge transport, and the voids between adjacent fibers are thoroughly accessible for electrolytes and bubble evolution. When evaluated as a positive electrode for wearable supercapattery, the hierarchical CoNi-LDH@PCPs electrode displayed high specific capacity and excellent flexibility. As oxygen evolution reaction (OER) catalyst, this PCPs-based electrode also reveals the lowest overpotential of 350 mV at 10 mA cm-2, and a Tafel slope of ∼58 mV dec-1. In addition, density functional theory (DFT) calculations suggest that the synthesis strategy for controllable tuning of hollow CoNi-LDH arrays reported here represents a critical step toward high performance electrodes for energy storage and electrochemical catalysis.