Chemometrics-assisted spectrophotometric methods were developed for simultaneous determinations of binary mixtures of (1). benzoic acid and salicylic acid, and (2). resorcinol and salicylic acid mixture ( whitefield ointment, luna soap, and dorin emulsion). The uv absorption spectra of the studied compounds in the range of 200-400 nm, showed considerable degrees of spectral overlapping (between 87.6% for benzoic acid and salicylic acid mixture, and 96.2% for salicylic acid and resorcinol mixture). The resolution of the mixtures have been successfully accomplished by using four techniques namely,1D (first derivative), 1D ratio, CLS (classical least square) and PCR (principal component regression). Validation parameters such as calibration range, LOD, LOQ, precision and accuracy parameters(Between F- and t-values respectively) were calculated and a comparison between all the methods and some official methods were done. The analysis is useful to professionals in pharmaceutical and chemical analysis fields in resolving binary or ternary mixtures having significant spectral overlapping.