Psychological capital (PsyCap) is a higher-order construct comprising hope, efficacy, optimism, and resiliency, which has attracted more and more attention from both academics and practitioners. Despite promising progress made in the PsyCap literature, the underlying mechanisms linking PsyCap to organizational outcomes still need more investigation utilizing longitudinal research design. Moreover, the reciprocal relationships between PsyCap and positive affect require more attention. Therefore, we aim to test the central role of positive affect in the relationships between PsyCap and affective organizational commitment (AOC) on one hand and organizational citizenship behaviour toward organization (OCBO) on the other hand as well as the reciprocal relationships between PsyCap and positive affect in this study. A three-wave longitudinal survey was conducted using a cross-lagged panel design with a one-month time lag between two consecutive waves. Panel data was collected from 208 workers in Beijing, China. The results support the hypothesis that positive affect serves as a mediator in the relationships between PsyCap and OCBO. Moreover, we also find some support for a reciprocal relationship between PsyCap and positive affect. The theoretical and practical implications of the findings are also discussed.