Interfacial adhesion between carbon fiber and epoxy resin mostly determine the mechanical properties of the carbon fiber/ epoxy composites and the chemical structures of epoxy resin and hardener plays an important role. In this regard, stereoisomerism of epoxy hardeners, such as 3,3′ and 4,4′-DDS (diaminodiphenylsulfone), can have significant influence on the fracture toughness of the cured epoxy and related carbon fiber composites. Therefore, this study aims to investigate the influence of stereoisomerism of epoxy hardeners on fracture toughness of the carbon fiber/epoxy composites. Triglycidyl aminophenol (TGAP) are selected as epoxy resin and 3,3′- and 4,4′-DDS are selected as epoxy hardener. Wetting behaviors and fiber matrix adhesion of TGAP/DDS mixtures onto carbon fiber are investigated and fracture toughness (KIC) of TGAP/ DDS mixtures are also investigated. Then, the mode II fracture toughness test of the carbon fiber/TGAP/DDS composites are carried out to investigate the influence of hardener stereoisomerism on fracture toughness of the resulting composites. Wetting and fiber matrix adhesion to carbon fiber of TGAP/3,3′-DDS was better than those of TGAP/4,4’-DDS and KIC of TGAP/3,3′-DDS was also better than that of TGAP/4,4′-DDS. As a result of the synergistic effect of better wetting, fiber matrix adhesion, and fracture toughness of TGAP/3,3′-DDS, the mode II fracture toughness of the carbon fiber/ TGAP/3,3’- DDS composites was almost twice of that of the carbon fiber/ TGAP/4,4′-DDS composites. Based on the results reported in this study, stereoisomerism of the epoxy hardeners can influence the fracture toughness of the resulting composites as well as that of the resin itself. In other words, only small difference, such as the spatial arrangement of the molecular structure of epoxy hardeners can cause huge difference in the mechanical properties of the resulting composites.