This work consists of a study about the influence of the fermentation methods on the resistant starch (RS) formation. Crystalline phases at the white bread after production and during the staling were evaluated. The bakery formulation was proportionally the same for the two fermentation methods used, except for the yeast. A commercial dry yeast and sourdough were used for the direct method (DM) and indirect method (IM), respectively. The temperature and cooking time, as well as the packaging and storage, were kept constant for all samples. Characterizations were performed on both samples by XRD and FTIR-ATR. It is possible to affirm that the fermentation method greatly influences the crystalline and microstructural properties of bread, mainly on the RS. The bread produced by IM presented more significant changes in its microstructure and degree of crystallinity than bread made by DM. These microstructural differences may be directly related to the microorganisms present in the sourdough, which can influence the bread resistant starch during the cooking and storage time.