Maize grain yield is considered to be highly associated with ear and leaf carbohydrate dynamics during the critical period bracketing silking and during the fast grain filling phase. However, a full understanding of how differences in N availability/plant N status influence carbohydrate dynamics and processes underlying yield formation remains elusive. Two field experiments were conducted to examine maize ear development, grain yield and the dynamics of carbohydrates in maize ear leaves and developing ears in response to differences in N availability. Increasing N availability stimulated ear growth during the critical two weeks bracketing silking and during the fast grain-filling phase, consequently resulting in greater maize grain yield. In ear leaves, sucrose and starch concentrations exhibited an obvious diurnal pattern at both silking and 20 days after silking, and N fertilization led to more carbon flux to sucrose biosynthesis than to starch accumulation. The elevated transcript abundance of key genes involved in starch biosynthesis and maltose export, as well as the sugar transporters (SWEETs) important for phloem loading, indicated greater starch turnover and sucrose export from leaves under N-fertilized conditions. In developing ears, N fertilization likely enhanced the cleavage of sucrose to glucose and fructose in the cob prior to and at silking and the synthesis from glucose and fructose to sucrose in the kernels after silking, and thus increasing kernel setting and filling. At the end, we propose a source-sink carbon partitioning framework to illustrates how N application influences carbon assimilation in leaves, transport, and conversions in developing reproductive tissues, ultimately leading to greater yield.