Accurate prediction of energy differences between alternative spin states of transition metal complexes is essential in computational (bio)inorganic chemistry-for example, in characterization of spin crossover materials and in the theoretical modeling of open-shell reaction mechanisms-but it remains one of the most compelling problems for quantum chemistry methods. A part of this challenge is to obtain reliable reference data for benchmark studies, as even the highest-level applicable methods are known to give divergent results. This Perspective discusses two possible approaches to method benchmarking for spin-state energetics: using either theoretically computed or experiment-derived reference data. With the focus on the latter approach, an extensive general review is provided for the available experimental data of spin-state energetics and their interpretations in the context of benchmark studies, targeting the possibility of back-correcting the vibrational effects and the influence of solvents or crystalline environments. With a growing amount of experience, these effects can be now not only qualitatively understood, but also quantitatively modeled, providing the way to derive nearly chemically accurate estimates of the electronic spin-state gaps to be used as benchmarks and advancing our understanding of the phenomena related to spin states in condensed phases.