We have investigated the influence of concentration of surfactants typically used as flotation frothers (α-terpineol and n-octanol) and roughness of the solid surface on phenomena occurring during rising bubble collisions with a model hydrophobic Teflon surface. The time of three-phase contact (TPC) formation (t(TPC)) and the time of drainage (t(D)) of the film formed between the colliding bubble and Teflon surfaces were determined using a high-speed camera working with a frequency 1040 Hz. The Teflon surface roughness was varied on a microscopic scale, within a roughness ranging between 1 and 100 μm. We have found that the roughness of the Teflon surface is a crucial factor of the kinetics of the TPC formation, both in the absence and in the presence of the surfactants. With the surface roughness increasing from ca. 1 to 80 μm the t(TPC) can be shortened by an order of magnitude, i.e. from 105 ms down to a few milliseconds. We have demonstrated that bouncing of the colliding bubble is responsible for the large differences in the times of TPC formation at the Teflon surfaces of different roughness. Low concentrations of α-terpineol and n-octanol caused a decrease in the t(TPC) with respect to distilled water. However, at high concentrations the t(TPC) was prolonged. The prolongation of the time of the TPC formation was dependent on the Teflon surface roughness and we have attributed this effect to different amounts of air present in the cavities and scratches of hydrophobic surfaces of different roughness. The mechanism of prolongation of the t(TPC) at high concentration of surface-active substances (frother overdosage) is proposed.