Boutique hotels, which belong to the hospitality sector, hold significance for guests seeking new experiences. Guests are interested in staying and spending money on boutique hotels that create memorable experiences. Based on previous studies in the boutique hotel industry, empirical studies have revealed several relationships without drawing upon stimulus–organism–response (S-O-R) theory. This study aims to fill an important gap by comprehensively examining the effects of the 4Es (educational, entertainment, esthetic, and escapist experiences) in the boutique hotel sector—along with the addition of memorable experience—with the assumption that ME powerfully generates an effect in eliciting positive emotions in customers. As a result, these positive emotions are expected to significantly influence customer loyalty intentions. Data were collected from Thai customers who had experiences with boutique hotels across four regions in Thailand: northern, northeastern, central, and southern. The researchers identified 12 boutique hotels, gathered data by selecting three hotels per region, and administered 50 questionnaires for each selected hotel. A total of 395 usable samples were then analyzed through structural equation modeling via SmartPLS. The findings enhance the theoretical understanding by making four contributions to the customer experiential concept in tourism and hospitality, providing valuable insights for both the management team and the operational staff of boutique hotel marketers.