Green consumption is critical for achieving sustainable development goals. Many studies have focused on explaining why customers choose green consumption, but rarely have scholars considered the significant impacts of the psychological costs. This study conducted an online survey of 677 sampled individuals in China. A structural equation model (SEM) was adopted to explore how three types of psychological costs (i.e., stress, stigma, and autonomy) moderate the indirect relationships of perceived hedonic value and perceived utilitarian value with green consumption (i.e., green purchasing, recycling, and refusing to use disposable products) through the willingness to pay a green premium (WPGP). The results show that perceived values can promote green consumption behaviours by increasing WPGP. In addition, the indirect benefit of perceived hedonic value was shown to be stronger than that of perceived utilitarian value. However, the direct association of perceived hedonic value with green consumption was shown to be weaker (compared to perceived utilitarian value) when the influence of WPGP was excluded. Moreover, the indirect associations of perceived hedonic value with green consumption were stronger among individuals with high stress than those with low stress. In contrast, the indirect associations of perceived utilitarian value on green consumption were weaker for people with high stigma than those with low stigma. However, no evidence was found to show that autonomy can moderate the indirect relationships. These findings emphasize the different mechanisms of perceived hedonic value and perceived utilitarian value on green consumption, as well as the moderating role of psychological costs in understanding the relationship between perceived value and green consumption. Accordingly, this study suggests that policymakers should highlight the hedonic value rather than the utilitarian when encouraging a green lifestyle that involves a green premium. This is particularly true of situations with a high level of customers’ psychological costs. However, if there is no way to further increase people’s WPGP, then promoting the utilitarian value should be used to promote green consumption.