Direct optical excitation of long-range charge-transfer (CT) states in organic photovoltaics is shown to be feasible, a fact that is ascribed to the very low but non-vanishing oscillator strength of each individual transition and the much higher density of states (DOS) as compared with their short-range counterparts. This finding provides a new framework to interpret the low-energy absorption spectra of photovoltaic devices and to correlate this property with the optoelectronic conversion process in working devices.