Improving energy efficiency is widely identified as shifting energy usage to an optimal status in order to ultimately strengthen a country’s competitiveness and development, and indeed this is of particular relevance to the Association of Southeast Asian Nations plus Six’ (ASEAN+6). The traditional data envelopment analysis (DEA) approach has extensively been employed for estimating energy efficiency, but it does not properly utilize the weight in the DEA model to probe the behavior change of a decision making unit (DMU). This research therefore applies a progressive time-weighted dynamic efficiency model (PTDEM) to estimate the energy efficiency of ASEAN+6 and discusses the issues concerning their energy decoupling rates and decarbonization. The proposed model herein fully considers a DMU’s behavior change by estimating its energy efficiency. Empirical results reveal that: (i) improvements in energy efficiency within ASEAN are greater than in the other six countries; (ii) members of ASEAN still have more room for improvement than the other six countries with regard to achieving the standard ratio of the energy decoupling rate; and (iii) there is no evidence of convergence to decarbonization within ASEAN+6.