Starch can be gelatinized during high pressure processing in the presence of water, but to a greater or lesser extent. Starch gelatinization is often accompanied by the formation of amylose complexes, in particular when a thermal treatment is used. Four different starches were considered in this study: potato, broad bean (Vicia faba), pea and tapioca. A comparison between high pressure-induced starch gelatinization (HPG) and conventional thermal gelatinization (TG) was made. In the case of broad bean starch, selected complexing molecules were considered for both thermal and high pressure treatments. Cross polarization/magic angle spinning (CP/MAS) 13C NMR, X-ray diffraction and thermal analysis were used to monitor physico-chemical changes in the structure and microstructure of starch preparations. Decanoic acid and carvacrol were selected as complexing agents to track the formation of amylose ligand complexes. It was observed that B-type starch (potato) was more resistant to pressure than the A-type starches (tapioca, broad bean and pea) considered in this study. The results showed that amylose ligand complexes were formed during high pressure treatment (20 min at 500 MPa at temperatures of 20 °C and 40 °C). Decanoic acid induced the complexing of amylose in the V6I type whatever the treatment used. On the other hand, the complexation of carvacrol appeared to depend on the temperature used during the high pressure treatment. It is assumed that carvacrol forms amorphous complexes with amylose during high pressure treatment. The amylose complexes were characterized by 13C CP/MAS NMR confirming the results obtained by X-ray analysis. Industrial relevance: Development of innovative assembly of amylose + molecules of interest (i.e. antioxidant) using a mild processing (40 °C) instead of 90 °C. At 90 °C, some molecules are damaged or oxidized. The use of high pressure permits the production of larger amount of compounds than using conventional thermal treatment. The main reason is that there is no need to solubilise the molecule of interest.