This paper has mainly studied chemical composition of clinopyroxenes from the kamafugitic series in Lixian County, West Qinling. The phenocrystal clinopyroxenes show complex types, complicated compositions, and multiple origins. The groundmass clinopyroxenes can be grouped into two pyroxene types: high-Ti aluminian diopside and Ti-bearing diopside which crystallized from the comagmatic melts. The substitution of CaTiAl2O6 for Ca(Mg, Fe)Si2O6 is common during the crystallization of diopsides, with the late melt rich in Ti and Al but poor in Si and Mg. Baicaoshan volcanic pipe is the product of an evolved magma with an evolutionary trend of Ti, Al, Fe, Na enrichment and Mg, Si depletion, which can be expressed by the substitution of CaTiAl2O6 and NaFe3+ Si2O6 for Ca(Mg, Fe)Si2O6 during the crystallization process of diopsides. The diopsides of this area are comparable with diopsides from kamafugitic series in typical areas of the world, showing that bulk composition of kamafugitic rocks provides constraints on mineralogical composition and crystal lattice features.