In this paper, the morphology and photophysical properties of non-woven and aligned ES nanofibers prepared from the ternary blends of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) / poly(2,3-dibutoxy-1,4-phenylene vinylene) (DB-PPV) / poly(methyl methacrylate) (PMMA) using a single-capillary spinneret are reported. Various PFO and DB-PPV phase-separated structures in the ES nanofibers were found by two different solvents: ellipsoidal DB-PPV (10-40 nm) and fiber-like PFO (20-40 nm) in the PMMA using chloroform, while fiber-like DB-PPV (10-20 nm) and fiber-like PFO (20-30 nm) using chlorobenzene. Such different PFO and DB-PPV structures resulted in various energy transfer/emission colors in the ES nanofibers. Moreover, highly aligned luminescence PFO/DB-PPV/PMMA blend ES nanofibers prepared from chlorobenzene showed a much higher polarized emission than the non-woven and the emission colors changed from blue to greenish-blue to green as the DB-PPV composition increased. The different polarized emission characteristics between PFO and DB-PPV in the ES nanofibers also led to varied emission colors at different angles. The present study suggests the morphologies and emission characteristics of the multicomponent ES nanofibers could be efficiently tuned through solvent types and blend ratios of semiconducting polymers.