Porous spherical LiMnPO4·2Li3V2(PO4)3/C composite was synthesized innovatively via spray-drying route using oxalate complex. X-ray diffraction patterns and energy dispersive X-ray results revealed that the composite was composed of LiMnPO4 and Li3V2(PO4)3. Scanning electron microscopy results revealed the porous spherical structure, and transmission electron microscopy (TEM) results exhibited that the surface of the microsphere was coated with carbon layer of about 5.1nm thickness. The mutual doping phenomenon between LiMnPO4 and Li3V2(PO4)3 was also confirmed by high resolution TEM and Fourier transform observation. Porous spherical LiMnPO4·2Li3V2(PO4)3/C delivered an initial capacity of 132.6mAhg−1 at 0.1C and noticeably enhanced high rate capacities at 1, 3 and 10C. Compared with solid spherical LiMnPO4·2Li3V2(PO4)3/C, cycle performance, high-rate performance and lithium ion intercalation performance of porous spherical LiMnPO4·2Li3V2(PO4)3/C were all significantly improved.