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This study examined how school climate and psychological capital influenced five types of teacher informal workplace learning (IWL) activities. The sample included 1296 teachers from Shanxi province, China. Of the five school climate dimensions examined, collaboration and instructional creativity had the most powerful effects. Decision making was positively related to learning through media and stakeholder interaction but negatively related to learning through colleague interaction and self-reflection. Psychological capital was a key mediator of the effects of school climate on IWL, reducing the negative effects of decision making and strengthening the positive effects of other dimensions of school climate.