The efficiency of photoinduced charge separation (CS) in electron donor-acceptor compounds is commonly limited due to fast deactivation processes, such as the excited-state internal conversion and ultrafast hot reverse electron transfer to the acceptor, charge recombination (CR). A traditional way to avoid undesired energy losses due to CR is to put the reverse electron transfer into the Marcus inverted region, thus effectively suppressing it. This method, however, is not generally applicable when considering CS from the second locally excited state because the driving force of CR to the first excited state is small, and thus charge recombination is ultrafast and efficient. In this paper, we study the kinetic features of CS/CR from the second locally excited state of the donor using a semiclassical stochastic model of electron transfer. Particular attention is paid to the CS efficiency as well as the influence of the polar environment and intramolecular high-frequency vibrational modes on the kinetics of the charge-separated state. The influence of a number of model parameters on the CS yield and the energy efficiency has been analyzed using the results of numerical simulations. Several simple practical recipes for creating molecular compounds with high CS yields have been suggested. Simulations have also revealed a strong and non-monotonous (double-humped) dependence of both the yield and energy efficiency of CS on the driving force.