Volatilization may represent a major dissipation pathway for pesticides applied to soils or crops, and these losses may be modified by soil surface conditions or in the presence of plant residues. This paper investigates the effect of surface conditions on volatilization through experimental results. The two experiments consisted of volatilization flux measurements for 3 days after an application of S-metolachlor together with benoxacor: one with two wind tunnels to compare the effect of the presence of crop residues on the soil on volatilization losses and another one at the field scale from bare soil without crop residues. Volatilization fluxes were large immediately after application (between 77 and 223 ng m−2 s−1 for S-metolachlor depending on experimental conditions), decreasing down to a few nanograms per square meter per second on the last day. Volatilization fluxes followed a diurnal cycle driven by environmental conditions. The losses found for both compounds were in accordance with their physicochemical properties. The crop residue on the soil surface modified soil surface conditions—primarily the soil water content essentially, the degradation of S-metolachlor, and the dynamics of volatilization loss.