The liquid–liquid immiscible flow and mass transfer were investigated in a novel Taylor–Couette microreactor (TCMR). Due to the rotation shear and microscale effects, each phase flowed in the form of helical strips/bands, instead of dispersion droplets as in conventional equipment. Based on the movement and inclination of the bands, the helical vortex (HV), mixed helical vortex (MHV) and stationary helical vortex (SHV) were distinguished. The characteristics of the regimes were strongly influenced by rotation speed and flow rate, but the specific surface area only slightly varied. The flow regimes also influenced the two phase mass transfer. It was shown that the mass transfer coefficient kLa monotonically increased with the rotation speed in the HV regime, while it slightly decreased when the flow shifted into the MHV/SHV regime. According to the parametric studies, empirical correlations were developed for the flow regime transition and mass transfer prediction.