Abstract— Understanding the fundamental crystal chemical controls on visible and near-infrared reflectance spectra of pyroxenes is critical to quantitatively assessing the mineral chemistry of pyroxenes viewed by remote sensing. This study focuses on the analysis of spectroscopic measurements of a comprehensive set of synthetic Mg-Fe pyroxenes from the visible through the near-infrared (0.3–2.6 μm) to address the constraints of crystal structure and Fe2+ content on spin-forbidden and spin-allowed crystal field absorptions in Ca-free orthopyroxenes. The chemistry and oxidation state of the synthetic pyroxenes are characterized. Coordinated Mössbauer spectroscopy is used to determine site occupancy of Fe2+ in the M1 and M2 crystallographic sites. Properties of visible and near-infrared absorption bands of the synthetic pyroxenes are quantified using the modified Gaussian model. The 1 and 2 μm spin-allowed crystal field absorption bands move regularly with increasing iron content, defining a much tighter trend than observed previously. A spin-allowed crystal field absorption band at 1.2 μm is explicitly verified, even at low total iron contents, indicating that some portion of Fe2+ resides in the M1 site. The 1.2 μm band intensifies and shifts to longer wavelengths with increasing iron content. At visible wavelengths, spin-forbidden crystal field absorptions are observed in all iron-bearing samples. The most prominent absorption near 506 nm, attributed to iron in the M2 site, shifts to slightly longer wavelengths with iron content. The purity and extent of this pyroxene series allows visible wavelength absorption bands to be directly assigned to specific transitions of Fe2+ in the M1 and M2 sites.