The objectives of this study were to investigate the wettability of orthodontic bracket material surfaces and the composition of salivary films adsorbed onto them after 30 and 60 minutes in vivo exposure. Specimens from stainless steel, fiber-reinforced polycarbonate, and polycrystalline alumina bracket manufacturing raw materials were subjected to (a) contact angle measurements with a homologous series of liquids, (b) micro multiple internal reflection Fourier transform infrared spectroscopy (microMIR FTIR) for the characterization of the molecular composition of the in vivo adsorbed groups, and (c) incident light optical microscopy of the acquired films. The highest critical surface tension was obtained from stainless steel (40.8 +/- 0.4 dynes/cm) followed by polycarbonate (32.8 +/- 1.3 dynes/cm) and alumina (29.0 +/- 0.9 dynes/cm), suggesting a higher potential for increased plaque-retaining capacity for the stainless steel brackets. Accordingly, the total work of adhesion and its polar and nonpolar components were consistent with the surface tension ranking. The nonpolar component of the work of adhesion was higher than its polar counterpart for all materials tested, implying a possible higher attachment prevalence for those microorganisms using dispersive forces, such as van der Waals forces, as the predominant attachment mechanism to surfaces. Qualitative and quantitative variations were observed in the adsorbed films after 30 and 60 minutes intraoral exposure that may reflect the influence of the surface properties of these substrates on the structure of the pellicle formed in vivo.