This paper presents a recent study on the morphology variation on the lateral faces of a HPHT diamond seed by MPCVD method. Raman spectroscopy and SEM were used to display the morphological and structural evolution of the grown diamond. It has been observed that different types of carbon allotropes were deposited at different heights of the substrate. At the bottom of the substrate, the feature of the lateral face was dominated by vertically aligned graphite nanoplatelets. An increment of sp3 and sp2 hybridized carbons was found to take over at the region of approximately 100 μm above from the bottom followed by the increasing-size diamond grains. The high quality single crystalline diamond was formed at the top of the lateral face. We proposed that the temperature gradient around the substrate is responsible for variable features on the substrate lateral face. By optimizing the growth temperature, we have obtained an enlarged area of the lateral face with high quality single crystalline diamond. This work will provide both sp2 on sp3 carbon materials for the development of electrochemical sensors and electrodes, and a foundation for the diamond lateral face growth with high quality and high purity.