This study investigated adhesion to dentin of a modified 4-META/MMA-TBB resin (4-methacryloxyethyl trimellitate anhydride in methyl methacrylate initiated by tri-n-butyl borane) which does not require PMMA powder to polymerize. Ground bovine dentin specimens were pre-treated with an aqueous solution of 10% citric acid and 3% ferric chloride (10-3). This solution removes the smear layer and demineralizes the dentin, exposing collagen. Improved bond strengths were obtained when a HEMA-primer was applied to 10-3 pre-treated dentin. SEM examination revealed the formation of a transitional zone of resin-reinforced-dentin (hybrid layer) in 10-3 pre-treated, HEMA-primed samples. The adhesive monomer impregnated exposed collagen fibrils and, upon polymerization, became entangled with them to create the hybrid layer, essential in achieving significantly high tensile bonding strengths. HEMA enhanced the penetration capability of dentinal substrates. After polymerization and formation of the hybrid layer, auto-cured acrylic resin, photo-cured composite and amalgam were all capable of adhering to the dentin. The modified 4-META/MMA-TBB resin created significant adhesive bonds to 10-3 pre-treated ground bovine dentin.