The molecular interaction between sildenafil citrate as electron donor and each of iodine; 7,7,8,8-tetracyanoquinodimethane (TCNQ); 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ); tetracyanoethylene (TCNE); 2,4,7-trinitro-9-fluorenon (TNF); chloranilic acid (CLA); chloranil (CL) and bromanil (BL) as acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studied and optimized. Beer’s law was obeyed in a concentration limit of 10–260 μg/mL for sildenafil citrate. For more accurate analysis, Ringbom optimum concentration range was found to be between 20–240 μg/mL. The limits of detection and determination were calculated and found to be 1.5 and 5.2 μg/mL, respectively. The standard deviations were calculated for different concentrations of sildenafil citrate using various acceptors. A Job’s plot of the absorbance versus the molar ratio of the sildenafil citrate to each of acceptors under consideration indicated (1:1) ratio. The proposed methods were found to be rapid, accurate, precise and sensitive and could be applied for determination of sildenafil citrate in pharmaceutical dosage forms (Viagra) without interferences from common additives encountered.