The aim of this study was to understand (i) the in vivo mastication behaviour of cooked black beans (chewing duration, texture perception, oral bolus particle size, microstructure, and salivary α-amylase) and (ii) the in vitro digestibility of starch and protein of in vivo-generated black bean oral bolus under simulated gastrointestinal condition. The beans were pre-treated using pulsed electric field (PEF) with and without calcium chloride (CaCl2) addition prior to cooking. The surface response model based on least square was used to optimise PEF processing condition in order to achieve the same texture properties of cooked legumes except for chewiness. In vivo mastication behaviour of the participants (n = 17) was characterized for the particle size of the resulting bolus, their salivary α-amylase activity, and the total chewing duration before the bolus was deemed ready for swallowing. In vitro starch and protein digestibility of the masticated bolus generated in vivo by each participant along the gastrointestinal phase were then studied. This study found two distinct groups of chewers—fast and slow chewers who masticated all black bean beans, on average, for <25 and >29 s, respectively, to achieve a bolus ready for swallowing. Longer durations of chewing resulted in boluses with small-sized particles (majorly composed of a higher number of broken-down cotyledons (2–5 mm2 particle size), fewer seed coats (5–13 mm2 particle size)), and higher activity of α-amylase. Therefore, slow chewers consistently exhibited a higher in vitro digestibility of both the starch and protein of processed black beans compared to fast chewers. Despite such distinct difference in the nutritional implication for both groups of chewers, the in vivo masticated oral bolus generated by fast chewers revealed that the processing conditions involving the PEF and addition of CaCl2 of black beans appeared to significantly (p < 0.05) enhance the in vitro digestibility of protein (by two-fold compared to untreated samples) without stimulating a considerable increase in the starch digestibility. These findings clearly demonstrated that the food structure of cooked black beans created through PEF treatment combined with masticatory action has the potential to modulate a faster hydrolysis of protein during gastrointestinal digestion, thus offering an opportunity to upgrade the quality of legume protein intake in the daily diet.