The structural control of block copolymer (BCP) particles, which determines their properties and utilities, is quite important. Understanding the structural relationship between solution-cast samples and polymer particles in a confined space is necessary to precisely regulate the internal structure of polymer particles. Therefore, a facile method by choosing an appropriate selective solvent is reported to prepare spherical polymer particles with ordered network structures. The rod-coil BCP, poly(dimethylsiloxane)-b-poly{2,5-bis[(4-methoxyphenyl)-oxycarbonyl]styrene} (PDMS-b-PMPCS), was chosen as a model polymer because of its strong phase segregation ability. First, the structures of the BCP with a thermodynamically stable lamellar structure cast from different selective solvents were systematically studied. Then, a polymer particle with the same internal structure as that of the solution-cast sample can be easily prepared by self-assembling in an emulsion confined space. The relatively large particle size is of importance in this process because the large value of the particle size to periodicity ratio can provide a weak confined environment. This method helps us understand the inherent self-assembling mechanism of polymer particles in an emulsion confined space and accurately control the internal structure of the polymer particle obtained.