This study reports the first time-resolved particle image velocimetry characterization of a planar two-phase mixing layer flow, whose velocity field is measured simultaneously in gas and liquid streams. Two parallel air and water flows meet downstream of a splitter plate, giving rise to an initially spanwise invariant configuration. The aim is to elucidate further the mechanisms leading to the flow breakup in gas-assisted atomization. The complete experimental characterization of the velocity field represents a database that could be used in data-driven reduced-order models to investigate the global behaviour of the flow system. After the analysis of a selected reference case, a parametric study of the flow behaviour is performed by varying the liquid ($Re_l$) and gas ($Re_g$) Reynolds numbers, and as a consequence also the gas-to-liquid dynamic pressure ratio ($M$), shedding light on both time-averaged (mean) and unsteady velocity fields. In the reference case, it is shown that the mean flow exhibits a wake region just downstream of the splitter plate, followed by the development of a mixing layer. By increasing both $Re_l$ and $Re_g$, the streamwise extent of the wake decreases and eventually vanishes, the flow resulting in a pure mixing layer regime. The spectral analysis of the normal-to-flow velocity fluctuations outlines different flow regimes by variation of the governing parameters, giving more insights into the global characteristics of the flow field. As a major result, it is found that at high $Re_g$ and $M$ values, the velocity fluctuations are characterized by low-frequency temporal oscillations synchronized in several locations within the flow field, which suggest the presence of a global mode of instability. The proper orthogonal decomposition of velocity fluctuations, performed in both gas and liquid phases, reveals finally that the synchronized oscillations are associated with a low-frequency dominant flapping mode of the gas–liquid interface. Higher-order modes correspond to interfacial wave structures travelling with the so-called Dimotakis velocity. For lower gas Reynolds numbers, the leading modes describe higher frequency fingers shedding at the interface.