The aim of this work was the determination of the basic optical parameters and electronic structure of conjugated polymer films by two commonly used techniques—spectrophotometry and ellipsometry. Poly(3-hexylthiophene (P3HT) and poly(3-octylthiophene (P3OT) conductive polymers films deposited on a glass substrate by the spin-coating technique showed very comparable surface structures composed of grains of similar sizes and shapes. X-ray tests confirmed that the polythiophene layers are amorphous, which confirmed the correctness of the choice of the optical models used. Selected optical models (Lorentz, Tauc–Lorentz and Cody–Lorentz) have been applied in order to determine the thickness, and optical parameters such as refractive index and extinction coefficient, absolute absorption and electronic parameters (energy gap Eg, amplitude A and broadening B). Spectral absorption determined from spectrophotometric measurement is similar to the absorption spectrum obtained from the ellipsometry method with the application of oscillator models.