Sensory perception of starch‐based products associates with salivary α‐amylase enzymatic activity. Besides this, other proteins relate to taste sensitivity and oral food processing. As such, the participation of different salivary constituents in starch‐rich food's sensory evaluation cannot be excluded. This study aims to identify salivary proteins altered by bread mastication and correlated with sensory ratings. In Experiment 1 the effect of bread mastication in α‐amylase enzymatic activity and SDS PAGE profiles between is assessed (N = 64). In Experiment 2, a sub‐sample of these individuals (N = 22) is subjected to sensory tests and the sensory ratings obtained are correlated with saliva protein composition. Salivary α‐amylase activity, in the supernatant of saliva collected after bread mastication, is negatively correlated with sweetness and saltiness ratings. Moreover, saltiness is positively correlated with the expression levels of carbonic anhydrase VI. Bread roughness presented a positive association with α‐amylase enzymatic activity and a negative association with S‐type cystatin expression levels. Despite further studies are needed to clarify the negative association between salivary amylase enzymatic activity and sweetness ratings, observed in this study, these results reinforce the role of α‐amylase and highlights that other salivary proteins can also influence starch‐based sensory perception.