In this investigation, the transient electroosmotic flow of multi-layer immiscible viscoelastic fluids in a slit microchannel is studied. Through an appropriate combination of the momentum equation with the rheological model for Maxwell fluids, an hyperbolic partial differential equation is obtained and semi-analytically solved by using the Laplace transform method to describe the velocity field. In the solution process, different electrostatic conditions and electro-viscous stresses have to be considered in the liquid-liquid interfaces due to the transported fluids content buffer solutions based on symmetrical electrolytes. By adopting a dimensionless mathematical model for the governing and constitutive equations, certain dimensionless parameters that control the start-up of electroosmotic flow appear, as the viscosity ratios, dielectric permittivity ratios, the density ratios, the relaxation times, the electrokinetic parameters and the potential differences. In the results, it is shown that the velocity exhibits an oscillatory behavior in the transient regime as a consequence of the competition between the viscous and elastic forces; also, the flow field is affected by the electrostatic conditions at the liquid-liquid interfaces, producing steep velocity gradients, and finally, the time to reach the steady-state is strongly dependent on the relaxation times, viscosity ratios and the number of fluid layers.