This work presents the synthesis of para-quinone methides (p-QMs), which were deposited as films using the high vacuum sublimation technique after being chemically characterized. The p-QMs films were characterized morphologically and structurally using scanning electron microscopy, atomic force microscopy, and X-ray diffraction. In addition, their optical behavior was studied by means of ultraviolet–visible spectroscopy, and the optical gaps obtained were in the range of 2.21–2.71 eV for indirect transitions, indicating the semiconductor behavior of the p-QMs. The above was verified through the manufacture and evaluation of the electrical behavior of rigid semiconductor devices, in which fluorine-doped tin oxide-coated glass slides (FTO) were used as an anode and substrate. Finally, as an original, ecological, and low-cost application, the FTO was replaced by substrates and anodes made from recycled Tetra Pak®, generating flexible semiconductor devices. Although the electrical current transported depends on the type of p-QMs, the substituent in its structure, and the morphology, the kinds of substrate and anode also influence the type of electrical behavior of the device. This current–voltage study demonstrates that p-QM2 with 4-Cl-Ph as a radical, p-QM3 with 4-Et2N-Ph as a radical, and p-QM6 with 5-(1,3-benzodioxol) as a radical can be used in optoelectronics as semiconductor films.