After the single structures of ferredoxin and ferredoxin-NADP+ reductase have been reported, no complex structure of them was reported. Here we report the crystallization of the electron transfer complex between ferredoxin and ferredoxin-NADP+ reductase from maize leaf and the structure analysis of this complex at 2.59 Å resolution. The structures of ferredoxin and ferredoxin-NADP+ reductase in this complex state differ from the structures of single states. The complex formation not only determines optimal orientation of the two proteins, but also contributes to modulation of the enzymatic properties.