Experimental and field studies have indicated that surfactants enhance oil recovery (EOR) in unconventional reservoirs. Rock surface wettability plays an important role in determining the efficacy of this EOR method. In these reservoirs, the initial wettability of the rock surface is especially important due to the extremely low porosity, permeability, and resulting proximity of fluids to the solid surface. This study is designed to investigate the effect of oil components, rock mineralogy, and brine salinity on rock surface wettability in unconventional shale oil/brine/rock systems. Six crude oils, seven reservoir rocks, and seven reservoir brine samples were studied. These oil samples were obtained from various shale reservoirs (light Eagle Ford, heavy Eagle Ford, Wolfcamp, Middle Bakken, and Three Forks) in the US. SARA (saturates, aromatics, resins and asphaltenes) analysis was conducted for each of the crude oil samples. Additionally, this study also aims to provide a guideline to standardize the rock sample aging protocol for surfactant-related laboratory experiments on shale reservoir samples. The included shale reservoir systems were all found to be oil-wet. Oil composition and brine salinity showed a greater effect on wettability as compared to rock mineralogy. Oil with a greater amount of aromatic and resin components and higher salinity rendered the surface more oil-wet. Rock samples with a higher quartz content were also observed to increase the oil-wetness. The combination of aromatic/resin and the quartz interaction resulted in an even more oil-wet system. These observations are explained by a mutual solubility/polarity concept. The minimum aging time required to achieve a statistically stable wettability state was 35 days according to Tukey’s analysis performed on more than 1100 contact angle measurements. Pre-wetting the surface with its corresponding brine was observed to render the rock surface more oil-wet.