Objectives: Surface conditioning of enamel and dentin is a key step during adhesive restorative procedures and strategies. The aim of this study was to investigate the effectiveness of five αhydroxy-acids (AHAs) as enamel and dentin surface etchants. Methods: Enamel and dentin specimens were prepared from human molars to determine the depth of demineralization by optical profilometry (Δz), the resin bond strength to enamel and dentin (μTBS), the micro-permeability of dentin-resin interfaces, and the gelatinolytic activity of dentin matrix induced by AHAs [glycolic (GA), lactic (LA), citric (CA), malic (MI) and tartaric (TA)] and controls [phosphoric (PA) and maleic (MA)]. All acids were prepared at 35% concentration. Adhesion studies employed Adper Single Bond Plus bonding system. Data were individually processed and analyzed by ANOVA, post-hoc tests and Pearson correlations (α=0.05). Results: AHA exhibited statistically lower depth of demineralization of enamel and dentin (average 4 fold) than controls (p<0.001). In enamel, MA and PA etching resulted in higher μTBS than AHA groups (p˂0.001). In dentin, GA, TA, CI and LA etching resulted in statistically similar μTBS than PA (p<0.05). The hybrid-layer (HL) thickness and interfacial micro-permeability intensity were statistically lower for AHA groups (p<0.05). A significant positive correlation was observed between the intensity of micro-permeability and the thickness of HL (p<0.05). AHA etchants elicited lower dentin enzymatic activity than controls (p<0.05).