Thermoplastic starch (TPS)/polycaprolactone (PCL) blends were obtained by melt mixing. First, the best formulation of thermoplastic starch (starch, plasticizer and additives) was studied. The obtained films were characterized by means of differential scanning calorimetry, DSC (melting temperature and crystallinity degree); thermogravimetric analysis, TGA (real composition of the blend and thermal stability); tensile tests (mechanical properties); infrared spectroscopy, FTIR (interactions between components); scanning electron microscopy, SEM (morphology); and water absorption tests. The effect of PCL/TPS ratio on the previously mentioned characteristics and properties were studied. In addition, the effect of using PCL modified with maleic anhydride as compatibilizer was also analyzed. An optimal compatibilizer content was found improving the mechanical properties and slowing down the degradation rate in soil of the blends. On the other hand, a slight increase in the water absorption of the blends was found in comparison with the noncompatibilized ones.