The aim of this study was to evaluate the ability of mid-infrared (MIR) spectroscopy combined with chemometrics to analyze unstimulated saliva as a method to predict satiety in healthy participants. This study also evaluated features in saliva that were related to individual perceptions of human–food interactions. The coefficient of determination (R2) and standard error in cross validation (SECV) for the prediction of satiety in all saliva samples were 0.62 and 225.7 satiety area under the curve (AUC), respectively. A correlation between saliva and satiety was found, however, the quantitative prediction of satiety using unstimulated saliva was not robust. Differences in the MIR spectra of saliva between low and high satiety groups, were observed in the following frequency ratios: 1542/2060 cm−1 (total protein), 1637/3097 cm−1 (α-amino acids), and 1637/616 (chlorides) cm−1. In addition, good to excellent models were obtained for the prediction of satiety groups defined as low or high satiety participants (R2 0.92 and SECV 0.10), demonstrating that this method could be used to identify low or high satiety perception types and to select participants for appetite studies. Although quantitative PLS calibration models were not achieved, a qualitative model for the prediction of low and high satiety perception types was obtained using PLS-DA. Furthermore, this study showed that it might be possible to evaluate human/food interactions using MIR spectroscopy as a rapid and cost-effective tool.