AbstractIn this work, initiated chemical vapor deposition (iCVD) has been employed as a one‐step liquid‐free process combining polymerization and coating for the encapsulation of 3D non‐planar substrates. Coatings have been applied using iCVD specifically to encapsulate microparticles of a highly water‐soluble crop protection compound (CPC) for controlled release. Release behavior has been compared among different coatings synthesized using different iCVD processing conditions, including varying degrees of polymer hydrophobicity, continuous and pulsed deposition, and crosslinking. iCVD has been found to provide tunable synthesis of hydrophobic, crosslinked polymers with control over mass diffusivity, and coating thickness for enhancing barrier properties.