Urbanization and industrialization have contributed to the rapid growth of solid waste production, posing serious challenges to the urban governance field. Consequently, the concept of “zero waste” (ZW) has gradually become the common goal pursued by human society. At the end of 2021, China initiated the second phase of ZW city (ZWC) construction. Several pilot areas were selected and these areas have exhibited the characteristics of regionalization in distribution. However, previous studies on China’s ZWCs have mainly summarized and reflected on the results of the first phase of practice, ignoring the development requirements of city cluster construction. The transformation from the ZWC to “zero-waste city clusters” (ZWCCs) requires the government, as a leader, to change its role to adapt to the new development trend. This study selects Shenzhen and the Pearl River Delta City Cluster (PRDCC) in the pilot cities as the research objects to discuss the successful experience of Shenzhen in terms of the improvement of the legal framework, establishment of a centralized park governance model, and establishment of an information platform. Based on the specific situation of the PRDCC, the study analyzes how the government should accomplish the transformation of its role and re-stablish its positioning. Furthermore, a case study reveals that the government should change its dominant role to a collaborator’s role to effectively promote ZWC construction, given the problems of unbalanced regional economic level, inconsistent solid waste treatment capacity, noncooperation among multiple subjects, and imperfect coordination mechanism. The study provides three recommendations for this purpose, including supporting enterprises and social organizations with institutional incentives and establishing a benign interaction model with multiple actors as well as a sound publicity and monitoring model. In conclusion, the transformation of China from ZWCs to ZWCC is in accordance with the development law, and the government must adapt to the law and change the governance model accordingly. The study provides a reference for ZWC construction in other countries or regions.