Electrospinning has been used widely for drug delivery applications due to its versatility and ease of modification of spun fiber properties. Net drug loading and release is typically limited by the inherent surface-area of the sample. In a relatively novel approach, sintering of electrospun fiber was used to create a capsule favoring long-term delivery. We showed that electrospun polycaprolactone (PCL) retained its initial morphology out to 1042 days of in vitro exposure, illustrating its potential for extended performance. Sintering decreased the electrospun pore size by 10- and 28-fold following 56 and 57 °C exposures, respectively. At 58 and 59 °C, the PCL capsules lost all apparent surface porosity, but entrapped pores were observed in the 58 °C cross-section. The use of Rhodamine B (RhB, 479.02 g mol-1), Rose Bengal (RB, 1017.64 g mol-1) and albumin-fluorescein isothiocyanate conjugate from bovine serum (BSA-FITC, ~66,000 g mol-1) as model compounds demonstrated that release (RhB > RB ≫ BSA-FITC) is controlled both by molecular weight and available porosity. Interestingly, the ranking of release following sintering was 57 > 56 > 59 > 58 °C; COMSOL simulations explored the effects of capsule wall thickness and porosity on release rate. It was hypothesized that model drug adsorption on the available fiber surface-area (57 versus 56 °C) and entrapped porosity (59 versus 58 °C) could have also attributed to the observed ranking of release rates. While the 56 and 57 °C exposures allowed the bulk of the release to occur in <1 day, the capsules sintered at 58 and 59 °C exhibited release that continued after 12 days of exposure.