Hollow structures on the submicrometer scale (nm) are obtained with the assembly of polyelectrolytes according to the layer-by-layer (LbL) technique. Following the LbL procedure, polymers alginate and chitosan were alternatively adsorbed on a vesicular template made of didodecyldimethylammonium bromide (DDAB). Evidence for the removal of the vesicular template entrapped in the alginate/chitosan film is presented. The removal of the vesicular template was achieved through interactions between a nonionic surfactant (Triton X100) and the double-chained surfactant forming the vesicles. The application of this approach allowed the production of hollow nanospheres with a mild procedure, avoiding the use of strong acids or other extreme working conditions that can modify the shell integrity. The obtained nanostructures were characterized by means of dynamic light scattering (DLS), the zeta potential, and scanning electron microscopy (SEM). The SEM analysis demonstrated the presence, after the core removal process, of nanocapsules indistinguishable in size and shape from the parent core-shell system. The analysis of the surface charge of the hollow nanocapsules, after the core dissolution, by zeta potential measurements, indicates good aggregate stability. DLS measurements showed that the size of the nanocapsules is on the order of hundreds of nanometers. Moreover, the size of both the core-shell and the hollow particles did not appear to be perturbed by variations in temperature or ionic strength.