The effects of a static external electric field on the ground state electronic structure of a porphine-quinone (PQ) complex have been studied by using density functional theory (DFT). The energies of the excited states have been calculated with time-dependent density functional theory (TDDFT) and with the approximate coupled cluster singles and doubles (CC2) method. The geometries of porphine and quinone have been optimized with B3LYP. The influence of the external electric field on the PQ complex has been studied at six different intermolecular distances between 2.5 and 5.0 Å with the BH&HLYP functional. An external electric field clearly affects the orbitals localized mostly on quinone but not the orbitals localized on porphine. Additionally, the effect of the external field increases with the increasing intermolecular distance. The optical absorption spectrum of porphine obtained by using the BH&HLYP functional is consistent with the Gouterman model and with the spectrum previously calculated with CAM-B3LYP. The potential energy curves of the Q and B states and the lowest charge transfer (CT) states of the PQ complex calculated by using the BH&HLYP with TDDFT functional have also been compared with those obtained with the CC2 method. Both methods show that the lowest CT state is clearly above the Q states when no external field is applied. Therefore, when the Q states of a porphine-quinone system are excited, the conical intersection is not possible and cannot thus provide a path for electron transfer (ET). The calculations show that the Q and B states are affected by the field much less than the lowest CT state. Consequently, the calculations show that the CT state crosses the Q and B states at certain field strengths. Thus, it is possible that the external electric field triggers ET in porphine-quinone systems via conical intersection.