Optical properties of vapor phase (VP) deposited and spin-coated fluorocarbon (FC) thin films on silicon substrates, such as refractive index, extinction coefficient and film thickness were characterized by a variable angle spectroscopic ellipsometry (VASE) in the range of 300–800 nm. A Lorentz model allows us to simulate the optical constants of the FC films with a minimum number of parameters while maintaining Kramers-Kronig (KK) consistency between the real and imaginary parts of the optical constants. FC films are nearly transparent over the visible spectrum, so it is possible to assume k (extinction coefficient) = 0 over part of the visible spectrum in a Cauchy model. To accurately simulate the obtained ellipsometric spectra, we performed a regression analysis in two steps assuming a three-phase and a four-phase model. The regression analysis was performed using the three-phase model and a best-fit mean-squared error (MSE) value of 1.717 (VP deposited FC film, Lorentz model) was obtained. However, the four-phase model was used to improve the best-fit result of 0.531 (VP deposited FC film, Lorentz model). The surface roughness layer was assumed to be a mixture of FC films and voids under the Bruggeman effective medium approximation (EMA). We found that the best-fit MSE was reduced when surface roughness was included.