This work presents a comparative study of the compatibilization of four binary blends with slight differences in their chemical structures. The natural polymers chitin (QA) and chitosan (QN) are blended with polyamide 6 (PA6) and polyamide 66 (PA66). The results, obtained using differential scanning calorimetry, infrared spectroscopy, and light and scanning electron microscopy, gave the following compatibilization sequence: PA6/QN approximate to PA66/QN > PA6/QA > PA66/QA. This behavior could be related to the ability of QN to form hydrogen bonds and also to the capability of the packing of PA66.