3D Printing Innovations in Polymeric Porous and Patterned Architecture

ABSTRACT Polymeric porous media are fundamental to sensing, thermal management, and filtration, yet traditional stochastic fabrication often forces trade‐offs between permeability and mechanical integrity. This review examines the paradigm shift from intrinsic chemical synthesis to extrinsic architectural programming, where the topology of “negative space” is treated as a precise design variable via additive manufacturing. We analyze this transition through four pivotal patterning strategies: (1) surface patterning, transforming passive boundaries into active electromechanical zones; (2) directional anisotropy, replacing random dispersion with vector‐dependent properties; (3) topological periodicity, utilizing lattice geometries to program mechanical metamaterials; and (4) hierarchical integration, decoupling conflicting functionalities across length scales. By synthesizing advances in vat photopolymerization and extrusion‐based printing, we demonstrate how these deterministic architectures enhance performance in multimodal sensing, soft actuation, thermal insulation, and selective filtration. Ultimately, bridging monolithic chemistry with biomimetic design offers a scalable pathway to adaptive, multifunctional material systems essential for addressing next‐generation structural and energy challenges.