This study is motivated by the preliminary direct numerical simulations in double-diffusive (DD) core-annular flows with slip at the wall which displayed elliptical shaped instability patterns as in a rigid pipe case; however, slip at the pipe wall delays the onset of instability for a range of parameters and increases the phase speed. This increased our curiosity to have a thorough understanding of the linear stability characteristics of the miscibleDDtwo-fluid flowin a pipe with slip at the pipewall. The present study, therefore, addresses the linear stability of viscosity-stratified core-annular Poiseuille flow of miscible fluids with matched density in a slippery pipe in the presence of two scalars diffusing at different rates. The physical mechanisms responsible for the occurrence of instabilities in the DD system are explained through an energy budget analysis. The differences and similarities between core-annular flow in a slippery pipe and in a plane channel with velocity slip at the walls are explored. The stability characteristics are significantly affected by the presence of slip. The diffusivity effect is non-monotonic in a DD system. A striking feature of instability is that only a band of wavenumbers is destabilized in the presence of moderate to large inertial effects. Both the longwave and shortwave are stabilized at small Reynolds numbers. Slip exhibits a dual role of stabilizing or destabilizing the flow. The preliminary direct numerical simulations confirm the predictions of the linear stability analysis. The present study reveals that it may be possible to control the instabilities in core-annular pressure driven pipe flows by imposing a velocity slip at the walls.