Digital Twin (DT) technology presents a transformative approach to retrofitting practices, with the potential of decarbonizing operating buildings (DOBs) by up to 30 %. However, the fragmented nature of the extensive International Organization for Standardization (ISO) guidelines for carbon assessment and the complexity of DT systems, hinder practitioners' efforts to fully realize DT's potential in achieving the 2050 zero-emission target for operating buildings. This is evident in the continuous increase in operational carbon emissions from buildings, which reached an all-time high of 10 gigatonnes (GtCO2) in 2022, and the mere 13 % global adoption rate of DT in building retrofitting. The aim of this review study is to develop a DT-driven Decarbonization Framework for Operating Buildings (DT-DeFOB) - a pathway for cohesive implementation of complex DT systems for DOBs. Using the inclusion and exclusion method, 243 relevant studies from 2018 to 2023 were selected for scientometrics mapping and systematic literature review (SLR). Furthermore, 20 ISO guidelines were selected for comprehensive document analysis. The findings indicated a growing trajectory in DT literature; however, a limited definitive trend in its effectiveness for DOB was evident. The SLR highlighted a lack of dynamic carbon criteria tailored for operating buildings, as well as a notable absence of a cohesive pathway for implementing multifaceted DT systems in DOBs. Hence, the critical components of DT-DeFOB were established, including a Dynamic Operational Carbon Reduction Guide (DOCReG) - a crucial component of DT-DeFOB developed via document analysis of the 20 selected ISO, Technology Interconnections, Human Engagement, Data Integration, and Lifecycle Management. DT-DeFOB provides a pioneering blueprint to help achieve the construction sector's 2050 net-zero carbon target, presenting a ground-breaking approach for impactful climate change mitigation strategies.