Specific, and precise spectrophotometric methods are developed and validated for the simultaneous determination of the binary antihypertensive mixture nebivolol hydrochloride and valsartan in the zero-order spectrum. The methods applied for the determination of this antihypertensive mixture are constant center spectrophotometric resolution technique, constant center spectrum subtraction resolution technique, and advanced concentration value. Nebivolol hydrochloride was determined by its zero order spectra at 280 and 213 nm while for valsartan it determined by its zero order spectra at 250 nm. All developed methods were applied for the determination of the cited drugs in the pharmaceutical formulation and the results obtained were statistically compared with each other and with those of the reported method. The comparison showed that there is no significant difference between the proposed methods and the reported method regarding both accuracy and precision.