A collection of sixteen different PPV's with an alternating substituent pattern and three reference compounds MEH-PPV (poly(2-methoxy-5-ethylhexyloxy-1,4phenylenevinylene)), CN-MEH-PPV (poly(2-methoxy-5-ethylhexyloxy- 1,4-phenylenecyanovinylene)) and P3HT (poly(3-hexylthiophene)) were studied by ultraviolet photoelectron spectroscopy on gold substrates and by optical absorption spectroscopy in solution. Together these two techniques were combined to give a picture of the uppermost part of the electronic structure of these materials and allowed for a comparison based on the molecular substitution pattern under the same experimental conditions.