The elastic response of chromium-tanned leather was successfully improved by treatment with XSBR, a carboxylated styrene-butadiene copolymer. The carboxylic groups pending from a styrene-butadiene rubber (SBR) backbone were found to promote penetration of the aqueous polymer dispersion into the fibrous tanned leather and participated in pH-reversible physical crosslinking by H-bonding. The different penetrations of XSBR or SBR were investigated using a micro-FTIR cross-sectional analysis from the grain (outer) to the flesh (inner) side of 18 wt% elastomer-treated samples, based on the shaved leather weight. In particular, the profile of the diagnostic out-of-plane =C-H bending of butadiene and styrene units was consistent with a more effective penetration of XSBR. The leather with XSBR showed a comparatively lower elastic modulus of 10–15% and roughly a 10% increase in elongation at the break, indicating better flexibility and shape recovery. Also, the leather was characterized by a 15% higher burst strength. These results suggest the better swelling of the ionomeric XSBR in the initial stage of retanning performed at a pH higher than the isoelectric point of the leather when both the tanned leather and the XSBR ionomer had a negative surface charge. The high pH favored the penetration of XSBR due to a poor attractive interaction with the tanned fibrous leather network. Subsequent processing in an acid bath caused further physical crosslinking through hydrogen bonding between XSBR and the leather.