Recent observations of the high-velocity impact response in poly (urethane urea), PUU, elastomers has inspired a new inquiry on whether enabling molecular mechanisms could benefit dynamic impedance optimization at the interface of a glass/polymer bilayer, particularly at the moment of impulse interaction. In this work, we investigate the molecular influence on dynamic impedance using microballistic measurements on two bulk elastomers, a PUU and a polyurea, PU. Upon impact at strain rates similar to 10(8)/s, PUU exhibits a moderate improvement in resistance against penetration than PU, that is more pronounced at higher speeds. The variation in dynamic stiffening corroborates well with the corresponding segmental dynamics data determined via broadband dielectric relaxation. Meanwhile, we calculate the shock impedance from the shock velocity data derived from the respective shock Hugoniot to discern the efficacy of dynamic impedance optimization between PUU and glass. New insight on molecular attributes will guide glass/polymer interface designs. Published by Elsevier Ltd.