The intensification mechanism of aqueous/organic phase reaction by the addition of magnetic polymer nanoparticles was investigated. To understand how nanoparticles intensify the liquid–liquid (L–L) reaction, three reaction enhancement strategies of mechanical agitation (MA), the addition of magnetic polymer nanoparticles (MPN) or phase transfer catalyst (PTC) were compared in Montanari oxidation system. A mass transfer mathematical model was established to describe the oxidation reaction process owing to its inherently fast characteristic of the oxidation of selected substrate (benzyl alcohol). Moreover, the influence of the nanoparticles concentration on the biphasic reaction was explored. The results indicate that the emulsification of nanoparticles is the main reason to intensify the L–L reaction, and the mass transfer specific surface area (aow) is a crucial factor to accelerate the reaction rate. In addition, the emulsion type also plays a significant role to influence the overall mass transfer coefficient (K) of substrate.