The sorption of three herbicides (alachlor, atrazine and linuron) on samples from six peats of progressive degree of maturity (fibric, hemic or sapric types) and soil samples (dryland agricultural Calcic Luvisol amended with the peats) was determined. The extent of the sorption was examined in terms of peat maturity (up to 220 analytical descriptors of the peat material). In most cases, a sorption enhancement effect was observed in the peat–soil system compared with the sum of the sorption in peat and soil alone, i.e., a positive interaction leading to an increase in soil matrix reactive sites. The analytical characteristics of humic and bitumen peat subfractions were useful in forecasting sorption performance. This was the case for high molecular weight hydrophobic fractions, the extent of the alkyl domain in humic substances and oxygen-containing groups. Correspondence analysis illustrated how different characteristics of the peats played a distinct role in sorption in the herbicide–peat system or in the soil–peat–herbicide system. In the former system, there was a relevant bearing of parameters indicating low peat maturity, whereas in the second the sorption was mainly explained by peat colloidal properties, including the concentration and base saturation of oxygen-containing functional groups.