The spectrophotometric characterization of high efficiency, optically-active samples such as light-emitting organic bulks and thin films can be problematic because their broad-band luminescence is detected together with the monochromatic transmitted and reflected signals, hence perturbing measurements of optical transmittance and reflectance at wavelengths within the photoexcitation band. As a matter of fact, most commercial spectrophotometers apply spectral filtering before the light beam reaches the sample, not after it. In this Report, we introduce and discuss the method we have developed to correct photometric spectra that are perturbed by photoluminescence.