Liquid-crystal 4-n-pentyl-4'-cyanobiphenyl (503) droplets dispersed in aqueous solution are prepared by the assembly of poly(styrenesulfonic acid) (PSSH) and poly(styrenesulfonate sodium) (PSSNa) at the 5CB/water interlace. The micrometer sized PSSH-coated 5CB droplets in the space confinement formed by two parallel glass slides break up into submicrometer sized droplets under evaporation-induced flow. We find that the size reduction of the PSSH-coated droplets is accompanied by the bipolar-to-radial configuration transition of the 5CB in the droplets, while the PSSNa-coated 5CB droplets show no size-dependent configuration transition in the same size range. Our results suggest that the size-dependent director configuration of liquid-crystal droplets encapsulated by polyelectrolytes can he modulated by changing the interface conditions, which is important in designing liquid-crystal droplets for optical and biological applications.