This paper presents the analytical solution of a combined electroosmotic and pressure driven flow of multilayer immiscible fluids in a narrow capillary. The mathematical model is based in the Poisson-Boltzmann equation and the modified Navier-Stokes equations. In the steady-state analysis, we consider different conditions at the interfaces between the fluids as potential differences, surface charge densities and electro-viscous stresses balances, which are discussed in detail. Results show the transport phenomena coupled in the description of velocity distribution, by the analyzing of the dimensionless parameters obtained, such as: potential differences, surface charge densities, electrokinetic parameters, term involving the external pressure gradient, ratios of viscosity and of dielectric permittivity. Here, the presence of a net electric charges balance at the interfaces breaks the continuity of the electric potential distributions and viscous shear stresses, modifying the flow field; thus, the electrical conditions established at the interfaces play an important role on the flow behavior. The present work, in which the velocity field is described, aims to be an important contribution in the development of theoretical models that provide a better understanding about labs-on-a-chip design.