Multi-molecular excited states accompanied by intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example, excimers or charge transfer states. Understanding the dynamics of these states is crucial to improve organic devices such as light emitting diodes and solar cells. Their full microscopic description, however, demands sophisticated tools such as ab initio quantum chemical calculations which come at the expense of high computational costs and are prone to errors by assumptions as well as iterative algorithmic procedures. Hence, the analysis of spectroscopic data is often conducted at a phenomenological level only. Here, we present a toolkit to analyze temperature dependent luminescence data and gain first insights into the relevant microscopic parameters of the molecular system at hand. By means of a Franck-Condon based approach considering a single effective inter-molecular vibrational mode and different potentials for the ground and excited state we are able to explain the luminescence spectra of such multi-molecular states. We demonstrate that by applying certain reasonable simplifications the luminescence of charge transfer states as well as excimers can be satisfactorily reproduced for temperatures ranging from cryogenics to above room temperature. We present a semi-classical and a quantum-mechanical description of our model and, for both cases, demonstrate its applicability by analyzing the temperature dependent luminescence of the amorphous donor-acceptor heterojunction tetraphenyldibenzoperiflanthene:C60 as well as polycrystalline zinc-phthalocyanine to reproduce the luminescence spectra and extract relevant system parameters such as the excimer binding energy.