Bio‐inspired catalysis for artificial photosynthesis has been widely studied for decades, in particular, with the purpose of using bio‐disposable and non‐toxic metals as building blocks. The characterisation of such catalysts has been achieved by using different kinds of spectroscopic methods, from X‐ray crystallography to NMR spectroscopy. An artificial Mn4CaO4 cubane cluster with dangling Mn4 was synthesised in 2015 [Zhang et al. Science 2015, 348, 690–693]; this cluster showed many structural similarities to that of the natural oxygen‐evolving complex. An accurate structural and spectroscopic comparison between the natural and artificial systems is highly relevant to understand the catalytic mechanism. Among data from different techniques, the differential FTIR spectra (Sn+1−Sn) of photosystem II are still lacking a complete interpretation. The availability of IR data of the artificial cluster offers a unique opportunity to assign absolute absorption spectra on a well‐defined and easier to interpret analogous moiety. The present work aims to investigate the novel inorganic compound as a model system for an oxygen‐evolving complex through measurement of its spectroscopic properties. The experimental results are compared with calculations by using a variety of theoretical methods (normal mode analysis, effective normal mode analysis) in the S1 state. We underline the similarities and the differences in the computational spectra based on atomistic models of Mn4CaO5 and Mn4CaO4 complexes.