Biodegradable fibers for the controlled delivery of anti-inflammatory agent dexamethasone were developed and studied. Mono and core-shell structure fiber are prepared by wet-spinning solutions of hydrophobic poly (lactide-co-glycolide) and hydrophilic alginic acid shell. The two model drugs, dexamethasone and dexamethasone-21-phosphate, were entrapped in core and shell, respectively. These fibers were characterized in terms of morphology, diameters, mechanical properties, in vitro degradation, and drug release. The optical microscopy and scanning electron microscopy photos revealed directly that fibers possessed core-shell structure. The release of dexamethasone and dexamethasone-21-phosphate was investigated, and the results showed that alginate shell retarded dexamethasone release significantly in both early and late stages. The core-shell structure fiber release shows a two stage release of dexamethasone and dexamethasone-21-phosphate with distinctly different release rates, and minimal initial burst release is observed. The results indicated that the prepared fibers are efficient carrier for both types of dexamethasone.