The electrochemical properties of a newly synthesised set of PPV derivatives were measured by cyclic voltammetry A new octyloxy substituted PPV derivative was first synthesised (POPV) The structure of the POPV is varied systematically by the replacement of the phenyl units by naphthyl and anthryl units and the effect of these variations on the electrochemical properties is explored The HOMO-LOMO levels of the polymers were determined from the onset potentials for the p-doping and n-doping scans From this the electrochemical bandgap for each of the polymers was calculated The systematic change in the structure of the POPV results in a systematic increase in the LOMO level of the polymer series whereas a concomitant increase in HOMO level results in an overall Increase in the bandgap of the polymers series The variation in the electrochemical optical properties and vibrational properties observed within the polymer series were all found to correlate with the structural changes made pointing towards structure property relationships and a guide to future synthetic strategies (C) 2010 Elsevier B V All rights reserved