Comb-like amphiphilic polymers SMA-g-MPEG, SMA-g-C12H25OH and SMA-g-MPEG C12H25OH were prepared with grafting poly(ethylene glycol)monomethyl ethers (MPEG) and laurel alcohol (C12H25OH) on poly(St-co-MA)(SMA). The results of FT-IR and 1H NMR confirmed success in the comb-like amphiphilic polymers preparation. The aqueous solubility of the as-prepared samples showed that SMA-g-MPEG could dissolved in water easily with transparent solution up to a mass concentration (ρ) of 100 g/L; the solubility of SMA-g-MPEG C12H25OH was slightly weak and a gel was formed at a concentration of 100 g/L; the solubility of SMA-g-C12H25OH was even bad and a gel was formed at a concentration of 60 g/L. Surface tension measurements indicated that at 25 ℃ the surface tension (?) of SMA-g-MPEG solution was decreased with the decrease of the concentration limitedly without the platform on the surface tension vs concentration curve; For the aqueous solution of SMA-g-MPEG C12H25OH, the surface activity was improved and its critical micelle concentration (CMC) could arrive at 4.22 g/L, in which its surface tension (γCMC) was 43.9 mN/m; SMA-g-C12H25OH gave excellent surface activity with a CMC of 1.21 g/L and a γCMC of 33.2 mN/m.