A simple method is presented to determine the thickness, refractive index and extinction coefficient of a film with the resolutions of ±1 nm, ±2 × 10-3, and 6 × 10-5, respectively. The method requires only ultraviolet-visible-near-infrared spectroscopy measurement of the transmittance of films with thicknesses of a few micrometers. A very small extinction coefficient of intermolecular charge transfer (CT) absorption of an exciplex-forming organic film is measured in the sub-bandgap wavelength region. This is to demonstrate that the CT absorption with extinction coefficient in the range of 10-3 to 10-5 can be measured indeed using the method, which is in the same resolution as photothermal deflection spectroscopy and Fourier transform photocurrent spectroscopy. The simplicity and feasibility of the proposed approach is expected to promote active study of intermolecular CT absorption in exciplex-forming films.