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Abstract We develop original flow-based methods to interrogate and manipulate out-of-equilibrium behaviour of ternary fluids systems at the small scale. In particular, we examine droplet and jet formation of ternary fluid systems in coaxial microchannels when an aqueous phase is injected into a solvent-rich oil phase using common fluids, such as ethanol for the aqueous phase, silicone oil for the oil phase and isopropanol for the solvent. Alcohols are often employed to impart oil and water properties with a myriad of practical uses as extractants, antiseptics, wetting agents, emulsifiers or biofuels. Here, we systematically examine the role of alcohol solvents on the hydrodynamic stability of aqueous–oil multiphase flows in square microchannels. Broad variations of flow rates and solvent concentration reveal a variety of intriguing droplet and jet flow regimes in the presence of spontaneous emulsification phenomena and significant mass transfer across the fluid interface. Typical flow patterns include dripping and jetting droplets, phase inversion and dynamic wetting and conjugate jets. Functional relationships are developed to model the evolution of multiphase flow characteristics with solvent concentration. This work provides insights into complex natural phenomena relevant to the application of microfluidic droplet systems to chemical assays as well as fluid measurement and characterisation technologies.