Strategies for the synthesis of a new class of porous and nonporous biodegradable microparticles (MPs) based on poly(d,l-lactic acid)-poly(ethylene glycol)-COOH (PDLLA-PEG-COOH) or poly(d,l-lactide-co-glycolide) (PLGA) copolymers have been investigated. Further, these MPs were coated with polyethylenimine (PEI) in order to compare the performance of the naked and PEI-capped MPs for the gas phase capture of model aldehyde volatile organic compounds (VOCs), hexanal and octanal. The removal efficiencies of the different MP formulations ranged from 50% reduction to 97% reduction of VOC vapors. By coupling the intrinsic gas adsorption properties of the parent, naked MPs with the potential for covalent capture by means of the PEI surface coating, we have generated new materials exhibiting a dual modality for VOC capture. These materials represent a new matrix for the remediation of VOCs based on renewable, sustainable polymers.