Measurements of Fe3+/∑Fe in geological materials have been intractable because of lack of access to appropriate facilities, the time-consuming nature of most analyses, and the lack of precision and reproducibility in most techniques. Accurate use of bulk Mössbauer spectroscopy is limited by largely unconstrained recoilless fraction (f), which is used to convert spectral peak area ratios into valid estimates of species concentrations and is unique to different mineral groups and compositions. Use of petrographic-scale synchrotron micro-XANES has been handicapped by the lack of a consistent model to relate spectral features to Fe3+/∑Fe. This paper addresses these two deficiencies, focusing specifically on a set of garnet group minerals. Variable-temperature Mössbauer spectra of the Fe2+-bearing almandine and Fe3+-bearing andradite end-members are used to characterize f in garnets, allowing Fe3+/∑Fe to be measured accurately. Mössbauer spectra of 19 garnets with varying composition were acquired and fit, producing a set of garnet-specific standards for Fe3+ analyses. High-resolution XANES data were then acquired from these and 15 additional previously studied samples to create a calibration suite representing a broad range of Fe3+ and garnet composition. Several previously proposed techniques for using simple linear regression methods to predict Fe3+/∑Fe were evaluated, along with the multivariate analysis technique of partial least-squares regression (PLS). Results show that PLS analysis of the entire XANES spectral region yields the most accurate predictions of Fe3+ in garnets with both robustness and generalizability. Together, these two techniques present reliable choices for bulk and microanalysis of garnet group minerals.