Background: This study aims to examine the characteristics of people who talk about suicide on Chinese microblogs (referred to as Weibo suicide communication (WSC)), and the psychological antecedents of such behaviors. Methods: An online survey was conducted on Weibo users. Differences in psychological and social demographic characteristics between those who exhibited WSC and those who did not were examined. Three theoretical models were proposed to explain the psychological mechanisms of WSC and their fitness was examined by Structural Equation Modeling (SEM). Results: 12.03% of our respondents exhibited WSC in the past 12 months. The WSC group was significantly younger and less educated, preferred using blogs and online forums for expressing themselves, and reported significantly greater suicide ideation, negative affectivity, and vulnerable personality compared to non-WSC users. SEM examinations found that Weibo users with higher negative affectivity or/and suicidal ideation, who were also using blogs and forums more, exhibited a significantly higher possibility of WSC. Conclusion: Weibo users who are at greater suicide risk are more likely to talk about suicide on Weibo. WSC is a sign of negative affectivity or suicide ideation, and should be responded to with emotional support and suicide prevention services.