Measurement of oxygen isotope ratios in common silicate minerals such as olivine, pyroxene, feldspar, garnet, and quartz is increasingly performed by Secondary Ion Mass Spectrometry (SIMS). However, certain mineral groups exhibit solid solution series, and the large compositional spectrum of these mineral phases will result in matrix effects during SIMS analysis. These matrix effects must be corrected through repeated analysis of compositionally similar standards to ensure accurate results. In order to widen the current applicability of SIMS to solid solution mineral groups in common igneous rocks, we performed SIMS homogeneity tests on new augite (NRM-AG-1) and enstatite (NRM-EN-2) reference materials sourced from Stromboli, Italy and Webster, North Carolina, respectively. Aliquots of the standard minerals were analysed by laser fluorination (LF) to establish their δ¹⁸O values. Repeated SIMS measurements were then performed on randomly oriented fragments of the same pyroxene crystals, which yielded a range in δ¹⁸O less than ± 0.42 and ± 0.58‰ (2σ) for NRM-AG-1 and NRM-EN-2, respectively. Homogeneity tests verified that NRM-AG-1 and NRM-EN-2 do not show any crystallographic orientation bias and that they are sufficiently homogeneous on the 20 μm scale to be used as routine mineral standards for SIMS δ¹⁸O analysis. We subsequently tested our new standard materials on recently erupted pyroxene crystals from Merapi volcano, Indonesia. The δ¹⁸O values for Merapi pyroxene obtained by SIMS (n = 204) agree within error with the LF-derived δ¹⁸O values for Merapi pyroxene but differ from bulk mineral and whole-rock data obtained by conventional fluorination. The bulk samples are offset to higher δ¹⁸O values as a result of incorporation of mineral and glass inclusions that in part reflects crustal contamination processes. The Merapi pyroxene SIMS data, in turn, display a frequency peak at 5.8‰, which allows us to estimate the δ¹⁸O value of the primary mafic magma at Merapi to ~ 6.1‰ when assuming closed system differentiation.