We report a simple evaporation process using liquid marbles as precursors to produce high sphericity, precisely diameter controlled polyelectrolyte microspheres. We use poly(diallyldimethylammonium chloride) (PDDA) as the test polyelectrolyte for this experimental study. We present measurements of the rate of mass loss during evaporation to demonstrate evidence of two limiting physical processes. At short times, the rate of mass loss is well described by the "D-2 law" regime, which is vapor diffusion limited. At long times, the rate of water diffusion inside the nearly solid polyelectrolyte microsphere becomes the rate-limiting step. The transition between these two limiting processes is accompanied by changes in the physical morphology inside the microsphere. We compare the estimated values of the water diffusion coefficients with the values reported in the literature to demonstrate good agreement.