Blends of poly (L-lactide) (PLLA) and poly (ε-caprolactone) (PCL) with and without paclitaxel were prepared via solution casting. DSC analysis as well as SEM analysis of the PLLA/PCL blend solution cast films showed that these blends are all phase separated.%PLLA crystallinity was found to increase with increasing PCL content (up till 15 wt.%). The PCL phase is found to homogeneously disperse in the PLLA matrix as spherical domains where the pore diameters of the PCL domains significantly increased with increasing PCL content. The degradation profiles matched with the slower degrading component PCL rather than PLLA and also increasing PCL content of the blends increased the degradation rate relatively. The increased crystallinity of the PLLA phase with increasing PCL contents confirmed that the degradation occurred through PCL phase. Cell proliferation on PLLA/PCL blends showed that all these blends were suitable for the support of cellular growth. Apoptosis assay with the paclitaxel-loaded PLLA/PCL blends showed an increase in cell death throughout 7 days of incubation where the cell death was increased with increasing PCL contents. This was attributed to the faster release of paclitaxel which was at least partially affected by the faster degradation rate at increasing PCL contents. The paclitaxel release was shown to be degradation controlled in the initial stages followed by a faster diffusion-controlled release in the later stages. These polymer blends were found to be very suitable paclitaxel release agents for which the paclitaxel release times can be altered with the composition of the blend and the film thickness.