Two simple and validated chromatographic studies were performed for simultaneous estimation of sildenafil citrate (SIL) and alfuzosin hydrochloride (ALF) in bulk, pharmaceuticals, and in the presence of their main degradation products. Two systems of mobile phase were applied isocratically for their first chromatographic separation using conventional and micellar mobile phases. Methanol, acetonitrile, and 0.02 M potassium dihydrogen phosphate (43:14:43 v/v; pH 4.66) were pumped at 1.3 mL/min in method I. Meanwhile, method II was based on less hazardous micellar mobile phase of nonionic surfactant (0.005 M Brij-35 in water; pH 2.5 adjusted with 0.1% orthophosphoric acid) with a flow rate of 1 mL/min. Both methods were carried on C18 column and coupled with UV detection at 225 nm at ambient temperature. The first method was rectilinear over the concentration range of 5–62.5 μg/mL for both drugs, while the second method showed higher linearity ranges of 0.5–40, 2.5–62.5 μg/mL for ALF and (SIL), respectively. The developed methods successfully enabled the quantification of the studied binary mixture in their tablets dosage form and evaluation their stabilities. Validation of the proposed methods according to ICH guidelines and system suitability were ascertained. Moreover, the applied methods were evaluated and compared from the perspective of green analytical chemistry, employing the National Environmental Methods Index, analytical Eco-Scale score, and Green Analytical Procedure Index, as three assessment tools.