Oscillating chemical reactions, encapsulated within artificial vesicles have been demonstrated as a powerful analogy of living cells for the investigation of chemical communication and morphogenesis. However, little is understood with regards to the influence of confinement on the reactivity of such systems. Herein, the effect of confinement on the Belousov–Zhabotinsky (BZ) oscillating reaction in bulk solution, (employing ferroin as a catalyst and malonic acid as the organic substrate) is investigated using scanning electrochemical microscopy (SECM) toward different insulating surfaces such as glass, silanized glass, or PTFE. An unexpected increase in the amplitude of the BZ reaction at a tip–substrate distance of ∼12–15 μm is observed. By simulating different reaction mechanisms, from simple EC′ catalysis to more sophisticated Oregonator or even an 11-reaction scheme, it is shown that such behavior reveals the intervention of redox catalysis processes and particularly the short-lived highly reactive radical intermediate BrO2• indirectly detected at micromolar concentrations. The reinspection of the EC′ mechanism shows that the homogeneous catalysis route is confirmed and kinetically characterized from SECM toward an insulating substrate, with promising potentiality in many systems. More specifically to the complex chemical case of BZ reactions, the mechanism is understood from the envelope curves of the oscillations, which are assessed in the absence of the oscillation (absence of organic substrate).