A series of well defined semifluorinated diblock copolymers of poly(1H, 1H-dihydroperfluorooctyl methacrylate)-block-polyethylene oxide (poly(FOMA-b-EO)) were used for the preparation of self-assembled structures. The morphologies of the poly(FOMA-b-EO) aggregates formed from solvent casting were investigated in terms of the copolymer composition, the concentrations of copolymer solutions, and the solvent type. From CHCl(3), the micellar film morphologies of poly(FOMA-b-EO(20k)) were found to be well-ordered spherical and interconnected rods aggregates when PFOMA block sizes were 10 k (or 20 k) and 80 k. The aggregates were also found to depend strongly on the copolymer concentration. On the other hand, the morphological phase of block copolymeric micelles was inverted in trichlorofluoromethane (CFC-11) solution which is a good solvent for PFOMA, and aggregates were formed with PFOMA as a corona and PEO as a core. Morphological variations were also achieved by using different solvents such as N,N-dimethylformamide (DMF) and methanol, where the aggregates formed were vesicles and lamella with rods.