The present review is mainly focused on the extended analysis of the results obtained from coupled measurement techniques of a thermal imaging camera and chronoamperometry for imines in undoped and doped states. This coupled technique allows to identify the currentvoltage characteristics of thin films based on imine, as well as to assess layer defects in thermal images. Additional analysis of results provides further information regarding sample parameters, such as resistance, conductivity, thermal resistance, and Joule power heat correlated with increasing temperature. As can be concluded from this review, it is possible not only to study material properties at the supramolecular level, but also to tune macroscopic properties of -conjugated systems. A detailed study of the structurethermoelectrical properties in a series of eight unsymmetrical and symmetrical imines for the field of optoelectronics and photovoltaics has been undertaken. Apart from this molecular engineering, the imines properties were also tuned by supramolecular engineering via protonation with camphorsulfonic acid and by creation of bulk-heterojunction compositions based on poly (4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl) and/or [6,6]phenyl-C71-butyric acid methyl ester, poly(3,4-ethylenedioxythiophene) towards the analysed donor or acceptor ability of imines in the active layer. The use of coupled measurement techniques of a thermal imaging camera and chronoamperometry allows obtaining comprehensive data on thermoelectric properties and defects indicating possible molecule rearrangement within the layer.