Nitroxide-mediated polymerization (NMP) is known to be a simple reversible deactivation radical polymerization (RDRP) method for preparing well defined polymers. In compared with other RDRP methods, NMP was highlighted by the clean and low toxic product which is favorable for some sensitive biological and electronic applications. Here we reported the first case of oxygen tolerance nitroxide-mediated miniemulsion polymerization, by introducing glucose oxidase (GOx) and ascorbic acid (AsAc) to the system. Without degassing treatment, the miniemulsion polymerization can be carried on using alkoxyamine 3-(((2-cyanopropan-2-yl)oxy) (cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile (Dispolreg 007) as the initiator. The oxygen tolerance NMP miniemulsion exhibited similar living and control behavior to the degassing system, and the chain extension could also be performed without degassing. The characteristics of this enzyme assisted oxygen tolerant heterogeneous NMP may provide exciting new opportunities for increased versatility of NMP polymerization in preparation of polymeric nano-objects.