Differently substituted benzyl bromides were synthesized by bromination from adequate benzyl alcohols. Compounds 3,4-dimethylbenzyl bromide, 3,5-dimethylbenzyl bromide, 4- phenoxybenzyl bromide, 4-(methylthio)benzyl bromide, 4-tert-butylbenzyl bromide, 4- methylbenzyl bromide and 4-phenylbenzyl bromide were synthesized with phosphorus tribromide, while 4-methoxybenzyl bromide was synthesized with acetyl bromide. Nuclear magnetic resonance (NMR) and Thin-layer chromatography (TLC) were carried out to determine the purity of the compounds. The solvolysis rate constants of synthesized benzyl bromides were determined conductometrically in ethanol at 25 °C. Solvolysis reaction constants for compounds which couldn`t be measured at 25 °C because od their lesser reactivity were determined at higher temperatures and later extrapolated to 25 °C. The measured values of the logarithms of reaction constants of solvolysis were correlated with the σ + -values of adequate substituents according to the Hammett-Brown correlation analysis. Two plots with different slopes were obtained where the first plot includes data for 4-metoxybenzyl bromide and 4-(methylthio)benzyl bromide, while the second plot is defined by the data which belongs to other compounds (4-phenoxybenzyl bromide, 3,4-dimethylbenzyl bromide, 4- methylbenzyl bromide, 4-tert-butylbenzyl bromide, 4-phenylbenzyl bromide and 3,5- dimethylbenzyl bromide). Each plot represents a separate mechanism of nucleophilic substitution in solvolysis of this bromide series. The value of the reaction constant ρ + (the slope of the plots) gives us a display of the charge change on the benzyl reaction site. The slopes of both plots have negative value which indicates a formation of a positive charge on the reaction center. The more negative value of ρ + for benzyls on the left plot (ρ1 + = −6,30) indicates the formation of a stable carbocation in the first step of an SN1 reaction. Lesser negative slope of the right plot (ρ2 + = −2,34) suggests an SN2 mechanism of belonging benzyl bromides. Therefore, the experiment has proven that 4-methoxybenzyl bromide and 4- (methylthio)benzyl bromide solvolyze in ethanol by SN1 mechanism, while 4-phenoxybenzyl bromide, 3,4-dimethylbenzyl bromide, 4-methylbenzyl bromide, 4-tert- butylbenzyl bromide, 4-phenylbenzyl bromide and 3,5-dimethylbenzyl bromide solvolyze by SN2 mechanism. Since 4-methoxybenzyl bromide has the highest absolute substituent σ + value and the highest reaction rate constant, the inital assumption that the solvolysis reaction of compounds with stronger electron-donating substitutents happens faster, was proven.