A water-based silsesquioxane (POSS)-containing polymer, POSS-PAA, was synthesized by using octavinyl-POSS (V-POSS) and acrylic acid (AA) via interfacial polymerization. The TEM of POSS-PAA showed that the polymer formed a core-shell structure in aqueous solution and was well-dispersed. The star-shaped POSS-PAA and linear PAA were both tanned with 3.5% chromium tanning agent, and leather hide was tanned with 3.5% chromium tanning agent as a control. The results showed that the shrinkage temperature of wet-blue leather treated by POSS-PAA was increased by 3.5 degrees C than that of the control. The thickening rate of the POSS-PAA treated wet-blue leather samples was increased by 21% and 96% than the linear PAA-treated leather and the control leather, respectively. The EDS results suggested that the POSS-PAA pre-treated leather had a higher chromium content than the others, and the chromium distribution from the leather flesh side to the grain side was uniform. Moreover, the Cr2O3 content in both the POSS-PAA and the PAA pre-treated tanning waste water was reduced by about 50%, compared to the control waste. The COD and BOD of the POSS-PAA pre-tanning waste were decreased compared to the others. Therefore, POSS-PAA appeared to be promising for promoting the development of cleaner leather production.