Starting flow due to a suddenly applied pressure gradient in a circular tube containing two immiscible fluids is solved using eigenfunction expansions. The orthogonality of the eigenfunctions is developed for the first time for circular composite regions. The problem, which is pertinent to flow lubricated by a less viscous near-wall fluid, depends on the ratio of the radius of the core region to that of the tube, and the ratios of dynamic and kinematic viscosities of the two fluids. In general, a higher lubricating effect will lead to a longer time for the starting transient to die out. The time development of velocity profile and slip length are examined for the starting flows of whole blood enveloped by plasma and water enveloped by air in a circular duct. Owing to a sharp contrast in viscosity, the starting transient duration for water/air flow can be ten times longer than that of blood/plasma flow. Also, the slip length exhibits a singularity in the course of the start-up. For blood with a thin plasma skimming layer, the singularity occurs very early, and hence for the most part of the start-up, the slip length is nearly a constant. For water lubricated by air of finite thickness, the singularity may occur at a time that is comparable to the transient duration of the start-up, and hence, an unsteady slip length has to be considered in this case.