A process for selectively removing photoresist, organic overlayers, and/or polymers/residues from a substrate without altering the surface chemistry and adhesion properties of the underlying substrate layers is provided. Generally, the process includes pretreating the substrate with hydrogen (e.g., by way of a hydrogen-based plasma) prior to deposition of a photoresist layer, and then ashing the substrate with a hydrogen-based plasma to selectively remove the photoresist, organic overlayers, and/or polymers/residues from the substrate during etching, post-etch, rework, etc. The hydrogen-based ashing process of the invention may be used post-etch to remove the residue photoresist, or may be used in a rework stripping process to remove misaligned patterns. The hydrogen-based ashing process following the initial hydrogen surface pretreatment substantially reduces surface chemistry poisoning, while retaining adequate adhesion properties following ashing.