Graphene is considered the most promising and revolutionary frontier material in the 21st century, thus both developed and emerging countries have accelerated the advanced deployment of graphene innovation strategies. However, the evaluation of technological potential and vacant technology in the graphene field is still missing in existing studies, leading to the problems of less decision-making information for the government and innovation subjects. To fill this gap, this study constructs a comprehensive framework for technological opportunity analysis based on the patent data mining method. According to this framework, the key graphene technologies are firstly identified, then the potential of these key graphene technologies is predicted, and vacant graphene technologies are also revealed to enlighten future directions of graphene technology. Results indicate that the identified 10 key graphene technologies include nano-film technology, composite material technology for vehicles, graphene composite material preparation technology, graphene reinforcing agents, lithium battery electrode technology, nanotechnology, cycle equipment processing, battery and fuel cell electrode technology, coating technology, and graphene conductive ink technology. Graphene nanotechnology and graphene composite material preparation technology are currently in the growth stage and maturation stage, respectively; and the remaining 8 key graphene technologies enter into the saturation stage. Furthermore, 25 vacant technology areas in the graphene field have been detected, and breakthrough measures such as changing material structure and improving experimental equipment could help achieve the innovation of vacant graphene technologies. The policy implications for the innovation of graphene technology are also provided in the end.