Climber species tend to provide various important ecosystem services within the habitat condition. Very little study was conducted on climber diversity, biomass, carbon (C) stock, and CO2 mitigation under urban setup. To address this research gap, the present study was conducted to evaluate the phytosociological attributes, diversity, climbing mode, host specificity, and their potential role in combating climate change. The study was carried out across the four directions of Ambikapur in various seasons using a random sampling method. Results revealed 11 species of climbers representing 9 families across the various study sites in different seasons. Most of the climber species were found to be herbaceous vine and woody wine in nature followed by the higher representation of stem twiner as climbing mode. Variation in species diversity across the study sites revealed higher value toward the west direction as reflected by the beta diversity value. Further, species richness and diversity were mostly reported from the east and north direction. The higher biomass, C stock, and mitigation value were recorded for the south direction in various seasons. Species such as Ampelocissus latifolia, Cuscuta reflexa, Cryptolepis buchanani, Ipomoea quamoclit, Mucuna pruriens, and Thladiantha cordifolia reflected higher biomass accumulation followed by C stock and greater CO2 mitigation potential among the observed climber species across various sites in various seasons. The present study highlights the importance of climber species under the urban ecosystem as a potential alternative for regulating the urban ambient environment followed by mitigation of changing climate.