This paper reports a series of new hole transport materials (HTMs) based on the two conformers of alpha,beta-dicyanostilbene (SCN) and alpha,beta-dialstilbene (SCO) with an emphasis on their optical and electrochemical properties. The calculations have been performed by density functional theory (DFT) and time-dependent density functional theory (TD-DFT) along with the Marcus theory. The frontier orbitals, Stokes shift, stability, reorganization energy, and hole mobility of the proposed materials have been obtained and discussed. The calculations show that the hole reorganization energy is much lower than the electron reorganization energy for our structures, indicating that this kind of materials can act as hole transport materials more efficiently than electron transport materials. All the designed structures have the ability to transfer holes and contribute to the photocurrent by the absorption of additional photons. This contribution is due to the fact that the absorption of these structures occurs in the 665.65-712.47 nm region where the perovskite absorption is very low. The obtained results for both conformers of SCN-NMe(2)DPA are really surprising. Accordingly, the hole mobility of the cis and trans conformers of this structure has the value of 1.75 x 10(-2) and 2.18 x 10(-2) cm(2) v(-1) s(-1), respectively which is about 7 and 9 times larger than that of spiro-OMeTAD as the most commonly used HTM. Moreover, the HOMO level of this structure (-5.22 eV) is 0.05 eV deeper than that of spiro-OMeTAD, making it more desirable for efficient usages. Based on these outcomes, it is expected that a device encompassing SCN-NMe(2)DPA as the hole transport material has larger open-circuit voltage (V-oc) and short-circuit current density (J(sc)) than the device with spiro-OMeTAD.