In spite of the pivotal role of excited state electronic structures as regulation of photoinduced electron transfer (PET) process, the effect of excited state conformation on PET remains elusive. Here we exploit distinguishable emission characters of trans and cis singlet excited states of donor-acceptor-donor ensemble MTPAAZO to reveal that its PET efficiency and rate are closely depended on its singlet excited state conformation. The PET process occurs solely in cis conformation of MTPAAZO singlet excited states. Novel molecule (MTPA)Ab as-designed with similar structure of MTPAAZO cis singlet excited states shows high PET efficacy and rate, leading to long-lived CS states. Our findings enable the rational design of the novel molecules with highly efficient PET process suitable for charge separation applications.