Indolizine has been synthesised on the small scale with enhanced yield using a novel Flash Vacuum Pyrolysis method. Electrooxidation of indolizine results in the formation of a redox-active film on the electrode surface. Excellent agreement is found between calculated and experimental indolizine oxidation potentials; a combination of fluorescence and electrochemical studies are consistent with the computational prediction that electroxidation results in the formation of three specific and redox active indolizine dimers. The insoluble redox active film is considered to be polymeric and to arise from the further oxidation of these dimers at the electrode. This combination of methods can be used for the characterisation of products formed from the electrooxidation of novel luminescent heteroaromatics synthesised on a small scale and particularly those of interest as redox active species for electrochemical processes and devices.