We have found that charge carriers can be generated by exciton-exciton annihilation in solid films of poly(di-[ital n]-hexylsilane). We use this phenomenon to study the kinetics of excitons at ambient temperature and show that the rate constant for exciton-exciton annihilation [gamma] is 2[times]10[sup [minus]7] cm[sup 3] s[sup [minus]1], in excellent agreement with the value we obtained previously by other means. The quantum efficiency for carrier production, at an electric field of 2[times]10[sup 5] V cm[sup [minus]1], is 1.3[times]10[sup [minus]3] per annihilation event. We also show that [gamma] is independent of the initial energy of the exciton state, even to energies far out on the long-wavelength tail of the exciton absorption band, and that the excitons remain mobile throughout their 600-ps lifetime.