The influence of the amino-, nitro-, methoxy-, hydroxy- and chloro-substituents in the ortho position towards the carboxylic group as well as alkali metal on molecular structure of benzoates was estimated. Optimized geometrical structures were calculated by B3LYP/6-311++G** method. Experimental FT-IR, FT-Raman and NMR spectra of the title compounds were recorded and analyzed. Data of chemical shifts in 1H and 13C NMR as well as wavenumbers and intensities in IR and Raman spectra of studied benzoate derivatives were analyzed in comparison with benzoic acid and with alkali metal benzoates.