The synthesis, morphology, and photophysical properties of poly[2,7-(9,9- dihexylfluorene)]-block-poly(2-vinyl pyridine) (PF-b-P2VP) with different coil lengths in mixed solvents of THF/methanol are reported. A flakes-like lamellar morphology is observed at a short coil length of PF-b-P2VP. As the coil length increases, a spherical and large compound micelle is formed. Upon further increase of the coil length, the morphological transformation from spherical micelles to long rod-like structures is observed. TGA results indicate a good thermal stability of the prepared copolymers. The spectra of optical absorption for the PF-b-P2VP in solution have a blue shift when the fraction of methanol in the mixed solvent increases. The present study shows that the significance of the rod/coil ratio and selective solvent content on the aggregate morphologies and photophysical properties of the rod-coil block copolymers.