UV‐VIS spectroelectrochemistry has been used to determine the formal potentials and n‐values of electrochemically polymerized conducting poly(heterolene) films. Ten polymeric compounds obtained from the monomers with different number of heterolene units, substitutions, and varying number of oxygen and sulfur moieties were studied. Trends for the change of formal potential values vs. the electronic excitation energies were obtained and discussed in several groups of related polymers. The effects of the number of rings and substitutions in monomer units on the spectral and electrochemical behavior of the polymers were investigated.