In this work, hollow fibers to be used as guides for tissue engineering applications were produced by dry-jet-wet spinning of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/poly(epsilon-caprolactone) (PHBHV/PCL) solutions in chloroform with various weight ratios between the components (PHBHV/PCL 100/0; 80/20; 60/40; 50/50; 40/60; 20/80; 0/100 w/w). Fibers obtained from PHBHV/PCL blends had a low degree of surface and bulk porosity, depending on composition. Physicochemical characterization involving scanning electron microscopy and differential scanning calorimetry (DSC) showed that PHBHV/PCL blends are compatible. Interactions between blend components were studied by Fourier transform infrared total reflectance spectroscopy, DSC analysis, and polarized optical microscopy analysis. Homogeneity of blend composition was assessed by IR-chemical imaging analysis. PHBHV/PCL samples were found to be weakly hydrophilic and their biocompatibility was proved by in vitro tests using mouse fibroblasts. Mechanical properties of PHBHV/PCL blends were investigated by stress-strain tests, showing an increasing ductility of blend samples with increasing PCL amount. Hollow fibers supported fibroblasts attachment and proliferation depending on composition and porosity degree.