In this study, the physicochemical, rheological, in vitro starch digestibility, and emulsifying properties of starch extracted from pineapple stem agricultural waste were investigated in comparison with commercial cassava, corn, and rice starches. Pineapple stem starch had the highest amylose content (30.82%), which contributed to the highest pasting temperature (90.22 °C) and the lowest paste viscosity. It had the highest gelatinization temperatures, gelatinization enthalpy, and retrogradation. Pineapple stem starch gel had the lowest freeze–thaw stability, as evidenced by the highest syneresis value of 53.39% after five freeze–thaw cycles. Steady flow tests showed that pineapple stem starch gel (6%,w/w) exhibited the lowest consistency coefficient (K) and the highest flow behavior index (n), while dynamic viscoelastic measurements gave the gel strength in the following order: rice > corn > pineapple stem > cassava starch gel. Interestingly, pineapple stem starch provided the highest slowly digestible starch (SDS) (48.84%) and resistant starch (RS) (15.77%) contents compared to other starches. The oil-in-water (O/W) emulsion stabilized with gelatinized pineapple stem starch exhibited higher emulsion stability than that stabilized with gelatinized cassava starch. Pineapple stem starch could therefore be used as a promising source of nutritional SDS and RS, and as an emulsion stabilizer for food applications.