Tissue engineered scaffolds should actively participate not only in structural support but also in functional tissue regeneration. Thus, novel smart biomaterial scaffolds have been developed, which incorporate a variety of bioactive molecules to accelerate neo-tissue formation. The effective delivery of multiple bioactive molecules with distinct kinetics to target sites at an appropriate concentration and in a timely manner is desired to drive tissue development to completion. To achieve effective, controllable delivery of multiple factors, a dual protein delivery system has been developed by electrospinning poly(lactide-co-glycolide) (PLGA) with different hydrophilicities. Bovine serum albumin or myoglobin was incorporated into and released gradually from these electrospun fibrous PLGA scaffolds. All the scaffolds exhibited similar loading efficiencies of approximately 80% of the target proteins. The introduction of Pluronic F-127 (PF127) dramatically increased scaffold hydrophilicity, which affected the release kinetics of these proteins from the scaffolds. Furthermore, distinct protein release patterns were achieved when using dual protein-loaded scaffolds with different hydrophilicities when these scaffolds were fabricated by co-electrospinning. This system may be useful as a method for delivering multiple bioactive vehicles for tissue engineering applications.