"Grafting from" surface-initiated atom transfer radical polymerization (ATRP) techniques were used to synthesize semifluorinated diblock copolymer brushes from silica substrates. Synthesis of either a polystyrene or poly(methyl acrylate) homopolymer brush was performed first (inner block) followed by polymerization of a semifluorinated monomer (outer block). The semifluorinated outer block consisted either of poly(pentafluorostyrene), poly(heptadecafluorodecyl acrylate), poly(pentafluoropropyl acrylate), or poly(trifluoroethyl acrylate). Analysis of the homopolymer and diblock copolymer brush layers was conducted using ellipsometry, ATR-FTIR, tensiometry, XPS, and AFM. Solvent-induced diblock rearrangement experiments were performed using a selective solvent for the hydrocarbon polymer block to generate a fluorine-deficient surface. With the exception of the systems containing PHFA, all the diblock systems were shown to exhibit water contact angles typical for the hydrocarbon polymer block after solvent treatment. Poor rearrangement for diblock copolymer brushes containing PHFA was observed when compared to all other semifluorinated diblock copolymer systems. The extent of diblock rearrangement was correlated to the calculated values for the solubility parameters of each block.