Cigarette smoking poses a major public health risk. Chatbots may serve as an accessible and useful tool to promote cessation due to their high accessibility and potential in facilitating long-term personalized interactions. To increase effectiveness and acceptability, there remains a need to identify and evaluate counseling strategies for these chatbots, an aspect that has not been comprehensively addressed in previous research. This study aims to identify effective counseling strategies for such chatbots to support smoking cessation. In addition, we sought to gain insights into smokers' expectations of and experiences with the chatbot. This mixed methods study incorporated a web-based experiment and semistructured interviews. Smokers (N=229) interacted with either a motivational interviewing (MI)-style (n=112, 48.9%) or a confrontational counseling-style (n=117, 51.1%) chatbot. Both cessation-related (ie, intention to quit and self-efficacy) and user experience-related outcomes (ie, engagement, therapeutic alliance, perceived empathy, and interaction satisfaction) were assessed. Semistructured interviews were conducted with 16 participants, 8 (50%) from each condition, and data were analyzed using thematic analysis. Results from a multivariate ANOVA showed that participants had a significantly higher overall rating for the MI (vs confrontational counseling) chatbot. Follow-up discriminant analysis revealed that the better perception of the MI chatbot was mostly explained by the user experience-related outcomes, with cessation-related outcomes playing a lesser role. Exploratory analyses indicated that smokers in both conditions reported increased intention to quit and self-efficacy after the chatbot interaction. Interview findings illustrated several constructs (eg, affective attitude and engagement) explaining people's previous expectations and timely and retrospective experience with the chatbot. The results confirmed that chatbots are a promising tool in motivating smoking cessation and the use of MI can improve user experience. We did not find extra support for MI to motivate cessation and have discussed possible reasons. Smokers expressed both relational and instrumental needs in the quitting process. Implications for future research and practice are discussed.