This work aims to experimentally investigate the elaborated nanocomposite based on the MEH‐PPV‐P3HT copolymer as a donor, which blended with the SWCNTs as an acceptor with different weight concentrations (1%, 3%, and 5% of SWCNTs). Various characterization techniques have been performed to analyze the effect of varying the SWCNTs' weight and the interaction between the two materials. The morphological and vibrational analysis were carried out using transmission electron microscopy (TEM) and Raman's spectroscopy, which indicate the dispersion of the SWCNT in the copolymer matrix. To analyze the optical properties, UV–visible, photoluminescence, and time‐resolved photoluminescence techniques have been used. To ascertain the influence of the SWCNTs addition, a comparative study between the resulting nanocomposite, basic copolymer, and various SWCNT concentrations has been examined. The results that have been accomplished demonstrate that the mixing between the copolymer MEH‐PPV‐P3HT and the SWCNTs reduces the band gap energy to be equal to 1.7 eV enhancing the charge transfer (CT) process and increases the absorption volume in the visible range. An increment in the average decay time compared to the MEH‐PPV‐P3HT has been noticed which improves the non‐radiative luminescence process. To analyze the intermolecular interaction, theoretical modeling using density functional theory (DFT) has been performed.