Poly(phenylquinoline)-block-poly(ethylene glycol)(PPQ-b-PEG) rod-coil block copolymers possess the self-assembly behavior in selective solvents. The copolymers in the mixed solvents of V(trifluoroacetic acid, TFA):V(dichloromethane, DCM)＝1:1 can self-assemble into polymer hollow microspheres with diameters of a few micrometers. The polymer hollow microspheres are monodisperse, and the diameters of them increase with an increased polymerization degree of the PPQ rigid-rod block. The solution concentration has no effect on the microsphere diameter, but spherical surface shows burrs when the solution concentration is too low. It has been found that the obtained dilute solution has the strongest absorption peak at 376 nm and strongest emission peak at 604 nm by the spectroscopy analysis.