Li/S and Li/air cells have attracted much recent attention as potential successors to lithium ion batteries because of their exceptionally high energy density compared with current battery technology. Although the two new battery systems have the potential to satisfy the demand for a significant leap forward in energy storage technology, there remain significant problems to be addressed, including poor cycle stability and low rate capability for practical applications. To address these issues, much research effort has been invested. In particular, graphene, with its high surface area combined with catalytic properties, is considered to be a key potential material to advance Li/S and Li/air battery technology. Indeed, recent research into graphene has led to substantial performance improvements of Li/S and Li/air batteries. In this review, we describe recent achievements in Li/S and Li/air cells that have been facilitated by the application of graphene, together with the electrochemical reaction mechanisms and major issues facing both Li/S and Li/air batteries.