With the rapid development of e-commerce, online shopping has become an indispensable part of people’s lives and unprecedentedly stimulates a paradoxical phenomenon—packaging pollution versus environmental protection. Therefore, it is necessary to discover a new relationship between green packaging and product brand from the consumer’s perspective in e-commerce. To address this issue, this paper proposes a theoretical framework to examine the impact of green packaging on brand attachment in e-commerce and identify the multiple mediation effects of perceived value, brand attitude, and trust. Study respondents comprising a total of 257 online consumers in China were observed, and the data analysis was executed via structural equation modeling. The results indicate that green packaging has a positive effect on perceived value and brand attitude, both of which can directly influence brand attachment and indirectly influence brand attachment positively through trust. Furthermore, by employing a bootstrapping method to confirm the mediation effect, it was found that perceived value and brand attitude can directly or indirectly mediate the positive relationship between green packaging and brand attachment. Therefore, this study implies that online merchants should pay considerable attention to the role of green packaging in brand attachment and formulate their green marketing plans based on the viewpoint of consumers.