In this work the ECD spectra of [5,10,15,20-tetrakis(2aminiumphenyl)-2,3,7,8,12,13,17,18-octaethylporphyrin complex with two (R)-camphorsulfonic acids were measured experimentally and computationally simulated as a test case for validating analytical approaches in chirogenesis. The following conclusions were made: 1) The search for conformers with the help of appropriate programs is much more reliable than a manual search, even in cases where the conformational space is significantly limited by the formation of hydrogen bonds. 2) Although NMR spectroscopy is a very helpful tool in structure determination, the conclusions drawn from only NMR measurements of supramolecular complexes can be erroneous. ECD spectra can provide more crucial, additional information about the relative positioning of supramolecule's moieties, and the best practice is to combine several measured spectra (in different solvents) with a computational study. 3) Conformational changes induced by rotation of the Et groups also affect the ECD spectra as they are involved in the formation of the cavity and determine the position of the guest, which, in turn, can affect the degree and mode of distortion of the porphyrin. 4) As ECD spectra are sensitive to a molecule's geometry it is important to consider the contribution of different conformers. In our case, this led to an accidental coincidence of the calculated spectrum with the experimental one in one of the solvents, although the structures were erroneous. In this case, simulation of the ECD spectra in different solvents can be helpful, even if their dielectric constants are close to each other. 5) We have also shown that the dominant conformer is sufficient to predict the ECD spectrum for complexes where the conformational landscape is limited by hydrogen bonding. The proposed analytical methodology can be a useful tool for comprehensive structural elucidation of complex artificial and natural supramolecular assemblies and has an immediate impact on understanding functional mechanisms of biological systems.