Olivine formation is directly related to Mg/Fe content. It is also significant in estimating the geological evolution of the moon. In this study, an estimation model of relative Mg number (Fo#) for lunar olivine was presented through multiple linear regression statistics. Sinus Iridum, the Copernicus Crater, and the pyroclastic deposit in the volcanic vents in the southeast of Orientale Basin were selected as the study areas. Olivine distribution was surveyed, and the relative Fo# calculation of olivine was implemented based on Moon Mineralogy Mapper (M3) data. Results demonstrated that olivine in the crater wall of Sinus Iridum and the Copernicus Crater had relatively high Fo#, which reflected the primitive melt. However, the difference in olivine spectral features between Sinus Iridum and the Copernicus Crater indicated different crystallization modes. The olivine in the pyroclastic deposit in the volcanic vents in the southwest of Orientale Basin also presented high Fo#, which indicated that the olivine was formed via rapid cooling crystallization and was accompanied by volcanic glass substances. As a result, the olivine relative Fo# calculated from the estimation model exhibited an important constraint implication for explanation of its causes.