This paper reports on the experimental and numerical analysis of the optical and thermal aspects of PCM (Phase Change Material) RT27 when subjected to an irradiation source of energy. The analysis is separated into the thermal and optical characterisation of the PCM using the T-history method and spectrophotometry principles, respectively, and the experimental and numerical performance evaluation of a PCM-Glazed unit. Various relationships describing the variations in the extinction, scattering and absorption coefficients with respect to the liquid fraction/ temperature within the phase change region were developed from the experimental setup, and were validated in a numerical CFD model. The results show that: i) during rapid phase changes, the transmittance spectra from the PCM are unstable, while under stable conditions a visible transmittance value of 90% and 40% are obtained for the liquid and phases, respectively; ii) the radiation scattering effects are more prominent in the solid phase of the PCM, while radiation absorption dominates in the liquid phase; iii) the optical/ radiation performance of PCM can be successfully modelled using the liquid fraction term as the main variable, in a similar way that the enthalpy porosity method is employed for phase change processes; iv) relative to a standard double glazed unit, the addition of PCM improves the thermal mass of the unit during phase change, but depending on specific