Hollow spheres have the potential for promising applications because of their advantageous properties, such as low effective density and high specific surface area.[1] In particular, they have been attracting increasing interest due to the possibility of their use in drug delivery, catalysis, paper coating, cosmetic foundations, and so forth. [2][3][4][5][6] Although there are many strategies for preparing hollow polymeric spheres, [7][8][9][10] a template is often needed. With the template method, hollow structures can be obtained after removing the template by dissolution, evaporation, or thermolysis. However, the preparation schemes are complicated or require large quantities of surfactants. Herein, we demonstrate a simple one-step method for fabricating hollow polymeric spheres with controllable size in aqueous media, by means of the droplet template formed by the monomer itself without the aid of surfactants or functional acids. Recently, polyaniline has been widely studied because of its special properties and potential applications in many fields. [11][12][13] Various morphologies such as nanotubes, [14][15][16] nanobelts, [17] nanofibers, [18][19][20][21] and hollow microspheres [22] have been reported using different strategies. Poly(o-toluidine) (POT), as one of the derivatives of polyaniline, has also received considerable attention. [23][24][25][26][27][28][29] Substituted derivatives of aniline are typically used to copolymerize with aniline to improve the processability of polyaniline, [30][31][32][33][34] while less attention is paid to controlling the morphology of polyaniline derivatives. [23,29] Here, we report for the first time the synthesis of POT hollow spheres in aqueous solution by the droplet template without surfactant stabilization. We found that hollow spheres could be obtained with sizes ranging from the nanometer to micrometer scales, simply by changing the concentration of o-toluidine. Interestingly, there is a hole in the surface of each synthesized POT hollow sphere and the size of the hole can be controlled by changing the molar ratio of initiator to monomer. Typical scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of POT hollow microspheres synthesized in aqueous solution are shown in Figure 1. The products are well-defined hollow structures and range in size from 1 to 8 lm, with an average diameter of 4 lm. It is clear from Figure 1a that there is typically just one hole in the surface of each microsphere; there are seldom two. These observations lead us to conclude that the POT microspheres are hollow. Their hollowness is further supported by using TEM (Fig. 1b). The TEM images of POT hollow spheres synthesized at different concentrations of o-toluidine are given in Figure 2. The sizes of the hollow POT spheres increase with the concentration of o-toluidine. When the concentration of o-toluidine is relatively low (e.g., 0.022 M), only hollow nanospheres ranging in size from 200 to 400 nm (Fig. 2a) are found, while hollow sub-micrometer-sized...