In one embodiment, a system for solvent annealing of a block copolymer film includes a solvent annealing chamber, and a controller configured to control at least one processing parameter for inducing a super-saturation of a solvent in an atmosphere within the solvent annealing chamber. In another embodiment, a method for solvent annealing of a block copolymer film includes inducing a super-saturation of a solvent in an atmosphere within a solvent annealing chamber having a block copolymer film therein for inducing formation of polymeric domains.