Understanding the relation between phase morphology and physical processes in polymer blends is the key to the fabrication of reproducible and reliable polymer optoelectronic devices. In this work, taking the advantage of low-temperature spectroscopy, we have observed the on-site generation of excitons and long-lived charges in different phase morphology polymer/fullerene blends. Probing at 10K, the photo-generated species are localized to where they are generated. We found that the generation of excitons and long-lived charges is highly influenced by the local molecular phase morphology. We further demonstrated that although the influence of phase morphology is localized to the place that excitons and long-lived charges are generated, this influence can persist over sub-millisecond timescales. Thus, we believe that the fate of excitons and long-lived charges is determined by the location at which they are generated, which can in turn be controlled precisely by molecular phase morphology.