The high yield of alkyl lactate from polysaccharides is attractive and challenging. Here, we report the remarkable catalytic ability of hierarchical tin-containing Beta zeolites for this process. The hierarchical structure, mediated by polystyrene microspheres or starch, improves mass transfer in the polysaccharide conversion. Two types of acidic sites in the zeolite achieved cooperation in the cascade conversion. Brønsted acid associated with Al promoted the hydrolysis of polysaccharides to monosaccharides; the abundant open Sn site stabilized by Ni2+ converted the monosaccharides to alkyl lactate. Polydextrose was used as a substrate in various alcohols, yielding up to 44% for methyl lactate, 37% for ethyl lactate, and 36% for propyl lactate, and the catalytic yields were consistent throughout three runs. More than 90% of the catalytic capability was recovered by the ion exchange and calcination procedures.