The interaction of 4-hydroxy-3-methoxybenzaldehyde (vanillin) and Hylon VII due to the formation of an inclusion complex is studied using Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), and circular dichroism (CD). The results confirm the close interaction among the different functional groups of vanillin and its host. In addition, a second case study was carried out with an amylose from a different source (100% amylose [APT III]). As a result, remarkable differences were found in the vanillin complexation capability of this amylose, which is only shown in solution by circular dichroism spectroscopy studies through a clear Cotton effect. This finding confirms the value of using CD studies, which shows that, depending on the amylose source, inclusion complexes can be found in solution, or both in solution and the coexisting precipitates, as shown using other techniques, such as X-ray diffraction (XRD) or differential scanning calorimetry (DSC). Moreover, solubility assays and complexation of both starches with iodine and subsequent absorption spectroscopy studies gives more information regarding the possible source of the starch encapsulation capability. Thus, Hylon VII shows higher capacity as vanillin encapsulant than APT III, showing the formation of inclusion complexes both in solution and solid phase, whereas APT III complexes are only perceivable in solution.