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This chapter explores the different ways in which solar radiation (SR) can be quantified for use in photovoltaic applications. Some solar radiation models that incorporate different combinations of parameters are presented. The parameters mostly used include the clearness index (Kt), the sunshine fraction (SF), cloud cover (CC) and air mass (m). Some of the models are linear while others are nonlinear. These models will be developed for the estimation of the direct (Hb) and diffuse (Hd) components of global solar radiation (H) on both the horizontal and tilted surfaces. Models to determine the optimal tilt and azimuthal angles for solar photovoltaic (PV) collectors in terms of geographical parameters are equally presented. The applicable, statistical evaluation models that ascertain the validity of the SR mathematical models are also highlighted.