The bean bug Riptortus pedestris is a major soybean pest and a cause of the stay-green symptoms. However, the molecular mechanisms underlying its olfaction-mediated host-seeking behavior remain unclear. In this study, we compared the antennae transcriptomes of starved and nonstarved adult R. pedestris, identifying four differentially expressed odorant receptor (OR) genes. Among these, RpedOR13 showed a strong response to the host volatile 2-phenylethanol (2-PE) in Xenopus oocyte assays, while electroantennography and behavioral tests confirmed 2-PE as an effective attractant. Next, phylogenetic analysis identified RpedOR72b as a paralog of RpedOR13, with subsequent Xenopus oocyte assays confirming its specific response to 2-PE. Additionally, RNA interference experiments highlighted the crucial role of RpedOR72b in detecting 2-PE. Taken together, these findings provide new insights into the molecular mechanisms of host-seeking behavior in R. pedestris and highlight the successful application of reverse chemical ecology in OR-based screening of bioactive compounds.