In this work, an experimental investigation of the single- and multiphase flows of two sets of fluids, CO2–ethanol and CO2–methanol, in a non-adiabatic microfluidic T-junction is presented. The operating conditions ranged from 7 to 18 MPa, and from 294 to 474 K. The feed mass fraction of CO2 in the mixtures was 0.95 and 0.87, respectively. Under these operating conditions, CO2 was either in liquid, gas or supercritical state; and the mixtures experienced a miscible single phase or a vapour–liquid equilibrium (VLE), with two separated phases. Taylor, annular and wavy were the two-phase flow regimes obtained in the VLE region. In the single phase region, the observed flows were classified into standard single-phase flows, “pseudo” two-phase flows and local phenomena in the T-junction. Flow regime maps were generated, based on temperature and pressure conditions. Two-phase flow void fractions and several parameters of Taylor flow were analysed. They showed a clear dependency on temperature, but were mostly insensitive to pressure. A continuous accumulation of liquid, either in the CO2 channel or at the CO2-side wall after the T-junction, disturbed most of the experiments in VLE conditions by randomly generating liquid plugs. This phenomenon is analysed, and capillary and wetting effects due to local Marangoni stresses are suggested as possible causes.