The aim of this study is to investigate the morphological and chemical changes of demineralized dentin collagen-matrix and resin/dentin interface associated with chitosan/riboflavin modification. Dentin disc specimens were prepared from sound molars, acid-etched with 35% phosphoric acid and modified with either 0.1% riboflavin or chitosan/riboflavin (Ch/RF ratios 1:4 or 1:1) and photo-activated by UVA. Morphological and chemical changes associated with surface modification were characterized by SEM and micro-Raman spectroscopy. Dentin surfaces of sound molars were exposed, acid-etched, and modified as described before. Etch-and-rinse dentin adhesive was applied, light-cured, and layered with resin-restorative composite. The resin infiltration and resin/dentin interface were characterized by micro-Raman spectroscopy and SEM. An open-intact collagen network-structure, formation of uniform hybrid-layer and higher resin infiltration were found with 0.1%RF and Ch/RF 1:4 modifications. Raman analysis revealed chemical changes and shifts in Amide bands with the modification of dentin collagen-matrix. The use of riboflavin and chitosan/riboflavin formulations to modify dentin-collagen matrix, with the defined ratios, stabilizes the collagen fibrillar network and enhances resin infiltration and hybrid layer formation. These preliminary results are encouraging for subsequent consideration of chitosan/riboflavin modification in adhesive dentistry. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2013.