A rare example of a ferromagnetically coupled dinuclear chromium(III) complex, the di-μ-hydroxobis[tetrakis(isothiocyanato)chromate(III)] anion, is reported. This complex has been synthesised from the oxo-bridged acetonitrile complex [(CH₃CN)₅CrOCr(NCCH₃)₅](BF₄)₄ and isolated as the solvated tetraphenylphosphonium salt, (Ph₄P)₄[(SCN)₄Cr(OH)₂Cr(NCS)₄]·2CH₃CN (1). From magnetometry the coupling constant, J, was determined to be -5.17 cm^-1 (in an H = JS_A·S_B scheme). The X-band EPR spectra were measured in the temperature range 2-305 K and the data were modelled. The spectra, which are very rich, are the first reported for a ferromagnetically coupled Cr-diol, and they allow for detailed modelling that encompasses zero-field splittings (ZFS) and fourth-order spin-Hamiltonian parameters for the coupled system. The structural parameters that determine the magnitude and sign of the exchange coupling were studied with broken-symmetry DFT. These results are discussed in terms of and compared to existing angular overlap model (AOM)-based magneto-structural correlations. This furnishes qualitative as well as quantitative insight into the coupling mechanisms.