In this study, poly(2-ethylhexyl acrylate) (PEHA) homopolymer and its copolymer combined with acrylic acid P(EHA-co-AA) were employed as interfaces in two separate Schottky structures. First, both interfaces were grown by initiated chemical vapor deposition (iCVD), which provides much better deposition control and homogeneous coating compared to solution-phase methods. In addition to this advantageous method, the effects of two different polymers, one of which is better able to adhere to the crystal surface on which it is formed than the other, on the optoelectronic properties have been studied. Then, their current-voltage (I-V) and capacitance/conductance-voltage (C/(G/ω)-V) characteristics were investigated both in the dark and under illumination. The basic electrical parameters and the illumination-induced profile of the surface state (Nss) were probed by I-V and C-V measurements for two samples. A decrease in the barrier height (BH) and, consequently, a significant increase in the photocurrent were observed under illumination. Striking changes in series resistance (Rs) values are also highlighted. The photocapacitance and conductance characteristics indicated that the structures could be considered not only as photodiodes but also as photocapacitors. Moreover, the voltage-dependent changes of some photodetector parameters, such as responsivity (R), sensitivity (S), and specific detectivity (D*), along with the transient photocurrent characteristics, are discussed for both structures. Therefore, we can say that the strong changes in these parameters, which figure the merit of photodiode and photodetector applications, depending on the voltage and under illumination, prove that it is a study carried out in accordance with the purpose and so they can be used in electronic and optoelectronic applications.