Regioregular poly(3-hexylthiophene) (rr-P3HT) is suitable for electronic noses and the detection of gaseous biomarkers of human diseases to clinical diagnosis. Nevertheless, thin-film properties such as crystallinity and thickness play a major role in overall device performance. Thin-films were obtained from spin coating of 2–20 mg/mL solutions in chloroform, toluene, chlorobenzene and dichlorobenzene to form a thickness from 20 to 160 nm as measured by atomic force microscopy (AFM). Absorbance spectrum fitted by the sum of three Gaussian curves defined the following parameters, which correlate with the film's electronic structure/morphology: (i) the abscissa at the center of the Gaussian from the highest wavelength, which responds for the P3HT band gap, and (ii) the ratio between the area under the Gaussian centered at the lowest wavelength over the one at the highest wavelength, which corresponds to the amount of amorphous and crystalline phase, respectively. Isosbestic point was determined by thermal annealing temperature variation, while keeping the thickness constant. It was observed that absorbance spectrum shape and, consequently, thin-film morphology depend not only on the concentration of the solution, but also on solvent. Finally, the isosbestic point determined at (470 ± 3) nm provides a linear relationship between absorbance and thickness with y-axis intercept approaching zero. The absorbance spectrum and isosbestic point of P3HT provides a non-destructive, faster and reliable way to estimate thin-film properties as thickness and crystallinity without recurring to AFM and X-ray diffraction (XRD) measurements.