Well-crystallized and regular lithium iron phosphate (LiFePO4) particles were synthesized via solvothermal reaction in H2O-isopropanol mixture solvents. FESEM micrographs indicated that the morphology of as-prepared LiFePO4 was strongly dependent on the conductive additives, i.e. when the additive changed from sucrose, carbon black to graphite, the LiFePO4 morphology changed from rod to square block. TEMand SAED results showed that rod-like LiFePO4 crystal grows along [201] direction preferentially. A rationalmechanismbased on the crystal growth prohibiting effect of additive was proposed. LiFePO4 sample with additive sucrose showed the best charge/discharge performance. It was able to deliver a high reversible capacity of 145.2 mAh·g-1 at 0.1C as well as a favorable capacity retention. Furthermore, it exhibited excellent rate performance and temperature performance. It could deliver 98.1 mAh·g-1 at 4C, about 67.6%of that at 0.1C, and the discharge voltage plateau still remained to be 3.12 V(vs Li/Li+).