The present article pays to some Alpine-Himalayan ophiolites of Late Cretaceous age from Darepahn area in the southern part of Nain-Baft Ophiolite belt. Whole rock processed data clearly shows that the metaperidotite rocks are silica-poor with low CaO, Al2O3, and TiO2 that reflect the predominance of olivine over calcic pyroxene in the protolithes. The considerable content of Co (85.6–124.6 ppm) and very low contents of Sc (4.3–15.3 ppm) and Sr (0.7-14 ppm) provided more evidence for olivine enrichment in the rock parentages. Calculating numbers of cation per formula unites based on EMPA results for distinguished Serpentine polymorphs (classified structurally via Raman spectroscopy) display that Tschermak substitution of trivalent cations for lizardite is tetrahedrally, and for chrysotile and antigorite, it is octahedrally. These chemical differentiations, lead to identifying chemical field plots in separator diagrams between SiO2, MgO, H2O, and Al2O3. Lizardite polymorphs can consider as primarily metasomatism results thru an iron-rich fluid occurrence. It has a considerable occupation of trivalent cations (especially Fe3+) and simultaneous less than 4 Si atoms in formula structure that reflected tetrahedral Tschermak substitutions. Antigorites have some deformed recrystallized textures along with high Σoct (Total Octahedral Cations) and low H2O content that could be considered as thermal originated polymorph. Chrysotiles have bimodal MgO and FeO contents that return to magnetite formations in groundmass and octahedral Tschermak substitutions on late-stage veins. The results exemplify compositional variations of Darepahn Serpentine polymorphs as a function of textural behaviors, structural position and thermodynamic condition of the formation process.