Highlights An asymmetric membrane electrode based on phosphorene/MXene heterostructure-textured nanopiezocomposite was fabricated via a polar urea-assisted self-assembly strategy and additive manufacturing of the heterostructure beyond the skin effect. The merits of this novel asymmetric heterostructure-textured electrode and its intrinsic piezoelectricity were detailedly discussed. The stepwise lithiation process of phosphorene was revealed, and the enhanced electrochemical properties of this phosphorene-based nanopiezocomposite textured electrode were verified by the improved cycling stability and kinetics.