The accuracy in electrical model parameters of solar photovoltaic (PV), such as photon current, the diode dark saturation current, series resistance, shunt resistance, and diode ideality factor, are desirable to predict the real performance characteristics of solar PV under varying environment conditions. First, this paper derives mathematical model of solar PV, in terms of two unknown, namely, series resistance and ideality factor. Then, using combination of analytical method, simulated annealing method, and derived model, a new parameter estimation technique has been proposed. Finally, performance indices, such as PV characteristics curve, relative maximum power error, root mean square deviation, and normalized root mean square deviation are estimated for the various solar PV panels, using proposed and existing methods, to reveal the effectiveness of the proposed method. Also, experimental data have been considered for the validation. Finally, through the comparative analysis of the results, it is revealed that the proposed method offers solar PV characteristics more closer to the real characteristics than the other existing methods.