Reverse water–gas shift (RWGS) reaction is a desirable strategy for achieving CO2 utilization and enhancing CO production. Due to the endothermic nature and the chemical equilibrium of this reaction, the reaction is typically conducted at high temperatures (300 ∼ 1000 °C); however, high temperature conditions lead to the sintering of the catalyst, resulting in a catalyst deactivation. Herein we report the synthesis of a metal oxide (V or Mo oxide)-decorated Pt nanoparticles encapsulated in hollow porous silica nanoreactors (HPSNs) by a W/O micro-emulsion system using branched poly(ethyleneimine) (PEI) as a sacrificial metal–ligand. The HPSNs encapsulating VOx-decorated Pt nanoparticles (Pt-VOx@HPSNs) afforded a 1.8-fold increased activity in RWGS reaction at 500 °C compared with Pt@HPSNs with a net CO production rate of 1140.3 mmol/gcat/h and with nearly 100 % CO selectivity. In situ XAFS measurement and reaction kinetic analysis reveal that the interplay of Pt nanoparticles and the decorated V oxide, which simultaneously activate H2 and CO2, respectively, leads to a lowering of the activation energy and a faster CO production rate. Furthermore, the Pt-VOx@HPSNs catalyst retains over 92 % activity after 50 h of continuous operation at 500 °C with the aid of a protective silica shell. This work offers a strategy for the design and development of an efficient and stable heterogeneous catalyst for RWGS reactions.