Abstract– Pyroxenes are among the most common minerals in the solar system and are ideally suited for remote geochemical analysis because of the sensitivity of their distinctive spectra to mineral composition. Fe2+ is responsible for the dominant pyroxene absorptions in the visible and near-infrared, but substitutions of other cations such as Ca2+ change the crystal structure and site geometries and thus the crystal field splitting energies of the Fe cations. To define spectral systematics resulting from major pyroxene cations (Ca2+, Mg2+, and Fe2+), we focus on a suite of pyroxenes synthesized with only Ca2+, Mg2+, and Fe2+ in the two octahedral sites, specifically examining the effect of Ca2+ on pyroxene absorption bands. The modified Gaussian model is used to deconvolve pyroxene spectra into component bands that can then be linked directly to crystal field absorptions. In orthopyroxenes and low-Ca clinopyroxenes, Ca2+-content has a strong and predictable effect on the positions of the absorption bands. At a threshold of Wo30, the crystal field environment stagnates and the M2 bands cease to change significantly as more Ca2+ is added. At Wo50, when most of the M2 sites are filled by Ca2+, band positions do not change drastically, although the presence and strengths of the 1 and 2 μm bands are affected by even trace amounts of Fe2+ in the M2 site. It is thus apparent that next-nearest neighbors and the distortions they impose on the pyroxene lattice affect the electronic states around the Fe2+ cations and control absorption band properties.