A new horseradish peroxidase (HRP)-catalyzed redox initiating system was successfully applied in the emulsion polymerization of styrene, producing stable polymer colloids and nanospheres. The particle size was about 30–50 nm with a diameter distribution (CV) 14–20% obtained by SEM. The molecular weight,
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\begin{document}$${\overline {\rm M}}{\rm n},$$\end{document} was around 105, and
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\begin{document}$${\overline {\rm M}}{\rm w}$$\end{document} was around 106. All the results were well consistent with the control, potassium persulfate (KPS)-initiating polymerization. The obtained experimental results supported a micelle mechanism similar to that of conventional emulsion polymerization of styrene.