A paucity of research investigates the heterogeneity in global R&D collaboration across climate change mitigation technological fields, limiting understanding of major players, inter-country relationships, and stimulus. Using co-inventive patent data obtained from the OECD.Stat for the period 2004–2018, this study applies social network analysis and exponential random graph models (ERGMs). The spatiotemporal dynamics and determinants of international R&D collaboration networks are investigated in the four major domains of CCMTs, namely, green energy (EGTD), green ICT (ICT), green transportation (TRANS), and green building (BUILD). Results reveal that while all four types of R&D networks share the characteristic of an obvious core-periphery structure, their core structures differ. BUILD and ICT have tri-polar worlds, with the former centered on the USA, China, and Germany, and the latter substituting Germany with India. TRANS maintains the bi-polar state led by the USA and Germany, whereas EGTD is the sole category that has evolved into a polycentric structure with hubs made up of developed and emerging countries. Path-dependence effects, hierarchy diffusion, and path breaking are embodied in networking mechanisms. In all technological fields, the top three triggers for collaborative networks are technology proximity, triadic closure, and bilateral trade, while the promotion effect of environmental regulation is emerging. Inter-country economic scale differences and language proximity exert waning effects on nearly all technological fields. North-South and South-South cooperation have much less influence on network evolution than North-North cooperation, and a diminishing tendency of South-South cooperation is particularly visible in BUILD.