To achieve a high photon-to-charge conversion efficiency, the electron–hole pair generated by photon absorption in organic photovoltaic systems must overcome the Coulomb attraction, which often results in voltage loss. Bearing this in mind, we performed ab initio time-domain simulations of the charge separation and energy relaxation across an interface formed by poly­(3-hexylthiophene) (P3HT) and a single-walled carbon nanotube (CNT). The dynamics of the positive and negative charges showed strong asymmetry. Photoexcitation of the polymer leads to a 100 fs electron transfer, in agreement with the experiment, followed by a loss of 0.6 eV of energy within 0.5 ps. Photoexcitation of the CNT leads to hole transfer, which requires nearly 2 ps, but loses only 0.3 eV of energy. The strong disparity arises due to the differences in the localization of the photoexcited donor states, the number densities of the acceptor states, and the phonon modes involved. Used as a chromophore, P3HT produces faster charge separation but leads to larger energy losses and cannot harvest light in the red region of the solar spectrum. In contrast, CNT absorbs a broader range of photons and reduces energy losses but gives a less efficient charge separation. The complementary properties of the two chromophores can be utilized to improve the performance of solar cells by optimizing simultaneously light harvesting, charge separation, and energy relaxation, which affect the photovoltaic yield, current, and voltage.