In order to realize controlled dual release of two hydrophobic drugs with distinct rates in a vehicle, novel poly(lactic-co- glycolic acid) (PLGA) composite nanofibers encapsulated with micelles were successfully fabricated by "emulsion-electrospinning." Brefeldin A (BFA) was firstly embedded in monomethoxy-poly(ethylene glycol)-b-poly(L-lactide) (MePEG-PLLA) micelles. By means of "emulsion-electrospinning," paclitaxel (PTX) and polymeric micelles contained BFA were successfully loaded into the electrospun PLGA composite nanofibers. The in vitro release results demonstrated that the location of the drugs in the electrospun fibers determined their release profiles. BFA had a long-term and sustained release while PTX had a relatively rapid release in the dual drugs delivery system. In vitro cytotoxicity studies revealed that the composite nanofibers with two drugs restrained HepG-2 cells more efficiently. These results strongly suggested that the electrospun composite nanofibers containing polymeric micelles can be used as an effective controlled dual release of hydrophobic drugs and were suitable for postoperative chemotherapy of cancers.