For development of the molecular solar-energy conversion systems, it is crucial to investigate how both the molecular geometry and electronic structure of electron donor-bridge-acceptor (D-B-A) molecules contribute to the electronic coupling for the charge-separation (CS) and charge-recombination (CR) processes. In a D-B-A system of a porphyrin-fullerene dyad (ZnP-C-60) bridged by a diphenyldisilane spacer, we have characterized one specific folded molecular conformation in the CS state among several existing conformations using the time-resolved electron paramagnetic resonance (TREPR) method at low temperature. To determine the molecular conformation and spin-spin exchange coupling of the CS state, we have considered (1) the electron spin polarization transfer from the excited triplet state of the C-60 moiety to the CS state and (2) the sublevel-selective spin relaxations and CR in the CS state. In the CS state of this conformation, although the ZnP cation and C-60 anion radicals are in close proximity, direct overlap between their singly occupied molecular orbitals is small, resulting in detection of the long-lived CS state which has a totally different conformation from the optically detected, charge-transfer (CT) complex. It has been demonstrated that, among several folded and extended molecular conformations created by the flexibility of the -Si-Si- bridge, the EPR conformation can play a role on the prevention of the energy-wasting CR.