Semiconductor nanocrystals are mostly prepared by colloid chemistry with organic surfactant molecules, and their surface polarization effect on the carrier relaxations are critical to their optoelectronic applications. Until now, the surface polarization effect and detailed photophysical processes of these capped quantum dots (QDs) are still unclear. Here, we studied the dynamics of the photoinduced carriers and capping molecule vibrations of capped CuInS2 quantum dots by using the femtosecond pump-probe system in both visible and IR zones. It is identified that the capping molecular vibrations exhibit significant Fermion bleaching nature, whose relaxation profile is in good agreement with the radiative recombination dynamics of QDs in the visible region. These results demonstrate that the extrinsic surface polarons form by the coupling of photoinduced carriers and surface ligand vibrations, and take part in the photophysical processes of these QDs. This finding is helpful for the QD design and applications in photoelectronic devices.