With the ever-growing demand for sustainability, designing polymeric materials using readily accessible feedstocks provides potential solutions to address the challenges in energy and environmental conservation. Complementing the prevailing strategy of varying chemical composition, engineering microstructures of polymer chains by precisely controlling their chain length distribution, main chain regio-/stereoregularity, monomer or segment sequence, and architecture creates a powerful toolbox to rapidly access diversified material properties. In this Perspective, we lay out recent advances in utilizing appropriately designed polymers in a wide range of applications such as plastic recycling, water purification, and solar energy storage and conversion. With decoupled structural parameters, these studies have established various microstructure−function relationships. Given the progress outlined here, we envision that the microstructure-engineering strategy will accelerate the design and optimization of polymeric materials to meet sustainability criteria.