Achieving control over the morphology of conjugated polymer (CP) blends at nanoscale is crucial for enhancing their performances in diverse organic optoelectronic devices, including thin film transistors, photovoltaics, and light emitting diodes. However, the complex CP chemical structures and intramolecular interactions often make such control difficult to implement. We demonstrate here that cooperative combination of non-covalent interactions, including hydrogen bonding, coordination interactions, and π-π interactions, etc., can be used to effectively define the morphology of CP blend films, in particular being able to achieve accurate spatial arrangement of nanoparticles within CP nanostructures. Through UV-vis absorption spectroscopy and transmission electron microscopy, we show strong attachment of fullerene molecules, CdSe quantum dots, and iron oxide nanoparticles, onto well-defined CP nanofibers. The resulting core/shell hybrid nanofibers exhibit well-defined donor/acceptor interface when employed in photovoltaic devices, which also contributes to enhanced charge separation and transport. These findings provide a facile new methodology of improving CP/nanoparticle interfacial properties and controlling blend morphology. The generality of this methodology demonstrated in current studies points to a new way of designing hybrid materials based on organic polymers and inorganic nanoparticles towards applications in modern electronic devices.