Two spectrometric methods have been developed for quantitative simultaneous determination of procaine hydrochloride (PH·HCl), procainamide hydrochloride (PHA·HCl) and lidocaine (Lid) from synthetic mixture. The methods employed are first derivative spectrometry, using zero crossing method and multicomponent analysis which is based on the additivity law. Using first derivative spectrometry, the wavelength selected for the quantitative determination of PH·HCl was 237 nm for Lid was 242 nm and for PHA·HCl was 290 nm in mixture. The method is linear when the concentration ranged between 6.62-9.93 μg/mL for PH·HCl, 6.43-9.64 for PHA·HCl and 5.56-8.35 for Lid. The multicomponent analysis is a direct method and involves the absorbance measurements of at three different wavelengths. The molar absorption coefficients values were calculated at each wavelength and the concentration of PH·HCl, PHA·HCl and Lid from mixture was determined by solving matrix using Cramer's rule. The recovery of each compound in mixture was calculated and it is 101.4 % for PH·HCl, 100.4 % for PHA·HCl and 98.4 % for Lid.