Drawing on the dual-systems theory (DST), this study proposes a research model that focuses on how the characteristics of the key opinion leader influence consumers’ purchase intention in live streaming commerce (LSC). We collected data through questionnaire surveys from samples of consumers in China (
N
= 467), which indicated that key opinion leader’s characteristics (i.e., attractiveness, trustworthiness, expertise) are all positively related to purchase intention. Importantly, the mediator analyses indicated that the effect of systems 1 on the relationship between attractiveness and purchase intention persisted is persistent, regardless of the type of goods purchased by the consumers (utilitarian or hedonic). This finding highlights the importance of attractiveness and reveals unconscious thought (UT) of consumers when shopping in LSC. This study provides a new theoretical perspective (i.e., DST) to identify attractiveness as a determinant of purchase intention in LSC and influence purchase intention by activating systems 1, thus solving the problem of identifying key factors in stimulus–organism–response theory. Besides, our results identify and test UT in LSC. The practical implications of these findings are to provide guidance for the selection of key opinion leaders in LSC and the development of live streaming industry.