The majority of native starch is used in the food sector and in the paper industry. Only a small amount is used in polymer engineering. One reason for the reluctance of the plastics processing industry to use starch as a filling material in polymer blends is the unsatisfactory mechanical behavior of starch when combined with thermoplastics. Another reason is the hydrophilicity of starch. In order to make these materials capable of competing, an amelioration of the mechanical properties is compulsory. By means of modifying the native starch and optimizing the compounding process, it is possible to improve the performance of starch blends, and, thus, increase the number of application areas of these materials. For this reason, native starch was modified with a cross-linking agent using a laboratory mixer. Subsequently, the modified starch and poly(lactic acid) were compounded using a co-rotating twin screw extruder. Cross-linking of the native starch in the laboratory mixer resulted in an increase in the mechanical strength of the starch blends. In addition, the blends with cross-linked starch displayed lower moisture absorption levels than blends with native starch as a filling material.