In the context of the drastic changes in the organizational competition, how to motivate employees to participate and exhibit voice behavior in organizational change is the key to successful change. In consideration of driving forces of voice behavior, most of the existing researches discuss the function of individual psychology and perceived organizational support separately, rather than their complementary or alternative role. In addition, under the background of change, the differences of mechanism of voice behavior are still unknown. In view of this, drawing on the theories of conservation of resource theory and perceived organizational support, the study develop a moderated mediation model to investigate the roles of openness to change and perceived organizational support that play in the relationship between psychological capital and voice behavior. We conduct a two-phrase survey on employees of companies located in Guangdong province and collect 292 useful data: psychological capital, perceived organizational support and openness to change in the first survey, and voice behavior in the second survey. Regression analysis and bootstrap methods are used to test the proposed model. The result of data analysis shows that: (1) psychological capital significantly and positively affects openness to change (β = .17, p < .01) and voice behavior (β = .39, p < .001); (2) openness to change partially mediates the relationship of psychological capital and voice behavior (β = .43, p < .001); (3) perceived organizational support positively moderates the psychological capital - openness to change relationship (β = .25, p < .001), that is, the higher level of perceived organizational support, the stronger positive relationship of psychological capital and openness to change, on the contrary, the relationship is weaker. Further, we draw an interaction picture to confirm the moderating effect of perceived organizational support on the relationship between psychological capital and openness to change. The mediating effect of openness to change is moderated by perceived organizational support as well. Overall, in order to better understand voice behavior in organizational change, this study develops a moderated mediation model to examine the complementary relationship of psychological capital and perceived organizational support and the mediation mechanism of openness to change. Theoretical contributions in this study may be included several aspects: (a) by investigating the driving factors of voice behavior in organizational change, our research fills the research gap of employee involvement in organizational change, but also expands the direction of research on voice behavior; (b) by identifying the mediating role of openness to change, our research uncovers the influencing path of psychological capital on voice behavior, and broadens the research of openness to change in China, given little focus on openness to change in China; (c) by examining the moderating role of perceived organizational support, our research offers a more comprehensive view of under what conditions that employees with high psychological capital are more likely to exhibit voice behavior. Inevitably, this study still has some limitations, such as defects caused by questionnaire and the slightly small sample size and so on. Scholars should try to overcome these problems as much as possible in future studies.