Core–sheath composite nanowires of LiMn x Fe1−x PO4 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) with vapor grown carbon fiber (VGCF) were synthesized by an electrospinning method. X-ray diffraction, SEM and TEM revealed that the electrospinning method could successfully fabricate a VGCF core at the nanowire-structured LiMn x Fe1−x PO4 sheath covered with an amorphous carbon layer. Furthermore, the spot patterns by selected area electron diffraction confirmed that LiMn x Fe1−x PO4 sheath consists of bundles of single-crystalline nanowire. The nanowire-structured electrode materials with uniformly dispersed carbon and highly crystalline active materials provided excellent rate capability.