This paper provides two main contributions: a new general formulation of radiation exergy and exergy efficiency of photovoltaic (PV) panels as grey surface absorbers; the development of an analytic method of radiative design of hybrid solar collectors by using matrix formalism.The new proposed GS (Gray Surface) model of exergy efficiency applicable for gray surfaces is proposed and compared with the classical models (in the first case study) and with its value of 0.939 reveals a difference of up to 1% compared with Petela-Landsberg-Press model (0.932) or Jeter-Carnot model (0.949).The new methodology is able to determine the thermal radiation losses through the lateral walls. The second case study includes an estimation of these losses at 2.63% for the analyzed design. A sensitivity analysis of thickness vs. exergy efficiency is performed, showing that each increase of the thickness of the collector by 10 mm determines a decrease of the extracted power (work) by 1.6% while the radiative exergy efficiency decreases by 0.75%.By including, in future research, the effect of the convection heat transfer, the proposed methodology could stand as a theoretical reference that can be compared with other two paths of research: numerical (CFD) and empirical.