Intrinsically fluorescent liquid crystals are highly sought after for a variety of applications. Most of the measurements of photo-physical properties of liquid crystals are made in dilute solutions, which is mainly due to the relative ease of both these measurements and the interpretation of data. The fluorescence spectra depend on a number of parameters including the concentration in liquid crystal solutions, the device geometry, and the mesophase in which the spectra have been measured. Working with neat, or concentrated, liquid crystal samples adds experimental complexities such as the inner filter effect (IFE), which affects the collection of data, interpretation of the results, and accuracy of the conclusions. In this paper, we present a systematic study of the photo-physical properties of both a model reference material, Nile red, and a nematic liquid crystal, 4-cyano-4′-pentylbiphenyl (5CB). The influence on the emission spectra of an increasing solute concentration is investigated and discussed. Moreover, a detailed investigation of the influence of the used device geometry, as well as the choice of appropriate data fitting methodologies, are presented.