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Introduction The use of e-cigarettes has become more common in China, but the research on e-cigarettes in China, while growing, is still limited. This study examined the characteristics and patterns of e-cigarette use, and analyzed the possible mediators between cigarette cessation intention and e-cigarette use in a Chinese smoking population. Methods This was a cross-sectional study conducted in mainland China. By convenience sampling method, the participants were recruited from 85 major commercial streets of several large cities in China. The study interviewers completed face-to-face interviews and uploaded the completed questionnaires into the online survey platform. The participants were contacted for clarification if any problems were detected. Logistic regression yielded adjusted odds ratios (ORs) for ever use of e-cigarettes. We further conducted a mediation analysis to estimate the effect of possible mediators. Results From July to August 2020, a total of 738 smokers were invited to participate in this study; 613 smokers were identified as eligible and 609 smokers were included in this analysis. Of them, 24 (3.94%) participants were currently using e-cigarettes, and 165 (27.09%) participants have ever used e-cigarettes. The participants with younger age were more likely to have ever used e-cigarettes, ranging from 37.5% in the 18–29 years age group to 6.5% in the 60–69 years age group. After controlling for demographic characteristics and nicotine dependence, the ever use of e-cigarettes was significantly associated with younger age, higher education level, higher monthly income, previous smoking cessation attempts and quitting intention. With the mediation analysis, the education level is confirmed as a mediating factor, and approximately 42.86% of the effects were mediated through the channel of higher socioeconomic status. Conclusions This is the first study to examine the possible mediators between cigarette cessation intention and e-cigarette use in a Chinese smoking population. The findings revealed that high socioeconomic status, particularly higher education level, was a major mediating factor.