Miscanthus is a perennial energy grass predominantly used for combustion but there is increasing interest in fermenting the cell-wall carbohydrates or green-cutting for soluble sugars to produce bioethanol. Our aims were to: (1) quantify non-structural carbohydrates (NSC), (2) observe the timing of seasonal shifts in the stems and rhizome, and (3) identify developmental and/or climatic conditions that promoted carbohydrate remobilization from the stems to the rhizome during senescence. Two genotypes of Miscanthus sinensis, a Miscanthus sacchariflorus and a Miscanthus × giganteus were grown at replicated field sites in Aberystwyth, West Wales and Harpenden, South East England. NSC were quantified from the rhizome and aboveground organs and then correlated with climatic data collected from on-site weather stations. PAR and maximum daily temperatures were higher at Harpenden throughout the year, but daily minimum temperatures were lower. Senescence was accelerated at Harpenden. Carbohydrates were retained within the stems of non-flowering genotypes, at both sites, in winter and were still present after a frost event to −2 °C. Rhizome starch concentrations were at least equal to the previous winter’s levels (February 2011) by September. Lower daily minimum temperatures accelerate the rate of senescence and warmer daily maximum temperatures cannot counteract this effect. At current yields, M. × giganteus, could produce 0.7 t ha−1 of NSC in addition to ligno-cellulosic biomass in November but with concerted breeding efforts this could be targeted for improvement as has been achieved in other crops. Shifting harvests forward to November would not leave the rhizome depleted of carbohydrates.