Electrospinning of cellulose nanocrystals (CNC)/poly(lactic acid) (PLA) emulsions has been demonstrated to be an effective dispersion and alignment method to control assembly of CNC into continuous composite ultrafine fibers. CNC-PLA nanocomposite random-fiber mats and aligned-fiber yarns were prepared by emulsion electrospinning. A dispersed phase of CNC aqueous suspension and an immiscible continuous phase of PLA solution comprised the CNC-PLA water-in-oil (W/O) emulsion system. Under a set of specific conditions, the as-spun composite ultrafine fibers assumed core-shell or hollow structures. In these structures, CNCs were aligned along the core in the core-shell case, or on the wall of the hollow cylinder in the hollow fiber case. CNCs act as nucleating agents influencing PLA crystallinity, and improve the strength and stiffness of electrospun composite fibers. The effects of emulsion droplet size on fiber structural formation and CNC distribution within the electrospun fibers have been carefully examined.