This paper presents the first experimental results on Marangoni–Bénard instability in a symmetrical three-layer system. A pure thermocapillary phenomenon has been observed by performing the experiment in a microgravity environment where buoyancy forces can be neglected. This configuration enables the hydrodynamic stability of two identical liquid–liquid interfaces subjected to a normal gradient of temperature to be studied. The flow is driven by one interface only and obeys the criterion based on the heat diffusivity ratio proposed by Scriven & Sternling (1959) and Smith (1966). The measured critical temperature difference for the onset of convection is compared to the value obtained from two-dimensional numerical simulations. The results of the simulations are in reasonable agreement with the velocimetry and the thermal experimental data for moderate supercriticality. Numerically and experimentally, the convective pattern exhibits a transition between different convective regimes for similar temperature gradients. Their common detailed features are discussed.