A time-dependent study on the formation of LiFePO4 with olivine-type structure is presented. The material is synthesized through a non-aqueous route in benzyl alcohol assisted by microwave radiation. The LiFePO4 forms with an anisotropic morphology of microscale stick-like particles. The detailed structure of these particles and their evolution with reaction time is revealed by transmission electron microscopy; a 3D reconstruction of a particle by electron tomography provides insight into the formation mechanism of these sticks. Without applying a thermal post-annealing treatment or a carbon coating, the electrochemical behavior of the LiFePO4 microsticks is assessed for the preparation of cathodes in lithium-ion batteries.