We demonstrate the use of commercially available fused silica capillary and fittings to construct a cell for operando X-ray absorption spectroscopy (XAS) for the study of heterogeneously catalyzed reactions under high pressure (up to 200 bars) and high temperature (up to 280 °C) conditions. As the first demonstration, the cell was used for CO2 hydrogenation reaction to examine the state of copper in a conventional Cu/ZnO/Al2O3 methanol synthesis catalyst. The active copper component of the catalyst was shown to remain in the metallic state under supercritical reaction conditions, at 200 bars and up to 260 °C. With the coiled heating system around the capillary, one can easily change the length of the capillary and control the amount of catalyst under investigation. With precise control of reactant(s) flow, the cell can mimic and serve as a conventional fixed-bed micro-reactor system to obtain reliable catalytic data. This high comparability of the reaction performance of the cell and laboratory reactors is crucial to gain insights into the nature of actual active sites under technologically relevant reaction conditions. The large length of the capillary can cause its bending upon heating when it is only fixed at both ends because of the thermal expansion. The degree of the bending can vary depending on the heating mode, and solutions to this problem are also presented. Furthermore, the cell is suitable for Raman studies, nowadays available at several beamlines for combined measurements. A concise study of CO2 phase behavior by Raman spectroscopy is presented to demonstrate a potential of the cell for combined XAS-Raman studies.