The extraction of p-, m- and o-nitrophenols with various ketones and esters was studied. The distribution constants of phenols between water and organic solvents were determined. The concentration constants of extraction of mononitrophenols were found to increase with reduced length of one of the alkyl radicals. So, the extraction constants decrease in the following series: acetates > propionates > other aliphatic esters and methyl n-alkyl ketones > di-n-alkyl ketones > diisoalkyl ketones. The extraction constants for cyclic ketones are the highest. This effect was explained in terms of decisive interference of steric hindrances in the constants of formation of hydrated solvates, the main species of p- and m-nitrophenols complexes extracted.