Green roofs (GRs) are a well-established green infrastructure (GI) strategy that have been extensively studied for decades to address a growing array of social and environmental challenges. Research efforts have been continuously made to contribute to the awareness of benefits of GRs and towards their widespread application. The substrate, which is one of the crucial layers of a GR system, plays a major role in the serviceability of GRs. Thus, several studies have been undertaken to alter the substrate characteristics by applying innovative substrate additives. Biochar, a carbon-rich material with a highly porous structure and large specific surface area, has been found advantageous in several areas such as agriculture, water filtration, environmental remediation, construction, and so on. However, the application of biochar in GRs has been insufficiently studied, partially because biochar amendment in GRs is a relatively recent innovation. Furthermore, a comprehensive review of the performance of biochar-amended GR substrates is lacking. This review paper aims to summarize the past performance of GRs enhanced with biochar by considering the various benefits that biochar offers. The results indicate that most of the reviewed studies observed increased retention of runoff and nutrients when utilizing biochar. Additionally, the capabilities of biochar in improving thermal insulation, plant performance, and microbial diversity, as well as its effectiveness in sequestrating carbon and controlling soil erosion, were mostly agreed upon. Notwithstanding, a definitive conclusion cannot yet be confidently made due to the limited research information from biochar–GR systems and the uneven research focus observed in the studies reviewed. The influence of biochar-related variables (including amendment rates, application methods, processed forms, and particle size) on the effectiveness of biochar was also discussed. Opportunities for future research were suggested to fill the research gaps and address challenges restricting the application of biochar in GRs. Detailed information from past research findings could serve as a foundation for further investigations into the large-scale implementation of biochar in GRs.