Zn-salt poly(styrene-ran-cinnamic acid) (SCA-Zn) ionomers were successfully synthesized via the melt neutralization of poly(styrene-ran-cinnamic acid) (SCA), which has a comparable molecular weight (M w = 217,000) to commercial polystyrene (PS), with different mass fractions of ZnO (0.62, 1.6, and 3.9 wt.%) and the successful synthesis was confirmed by Fourier transform infrared spectroscopy. The mechanical properties, heat resistance, and processibility of the PS, SCA, and SCA-Zn samples were characterized. Compared to SCA, the three SCA-Zn ionomers exhibited significantly higher α cN values, with the ionomers containing 1.6 and 3.9 wt.% ZnO were 11.4% and 68.6% higher than that of SCA, respectively. Compared to commercial PS, SCA-Zn also exhibited significant improvements in heat resistance (glass transition temperature and vicat softening temperature both improved by about 20 C) and impact toughness (α cN values of the ionomers containing 1.6 and 3.9 wt.% ZnO were 69.6% and 156.5% higher than that of PS), while the processability of SCA-Zn was not significantly worse than that of PS. This method efficiently improves both the toughness and heat resistance of PS, providing an efficient way to expand the market application of styrenic resins.