Unique starlike CdS particles were prepared from the lyotropic triblock copolymer solution system. The starlike CdS consists of a spherical core and dozens of the attached conical nanolobes. From the comparative studies with the spherical and rod-shaped CdS nanoparticles, the unique photophysical property is presented for the starlike CdS particle. The experimental results suggest that the photogenerated charge carriers at the tip-edge region of the conical nanolobe in the starlike CdS system diffuse into the thicker inner part including the core region, which is possibly due to the decreasing excited state potential gradient from the tip edge to the thicker inner part. This type of charge carrier diffusion dynamics from the surrounding to the thicker inner part in this anisotropic morphology of the starlike CdS semiconductor closely resembles the energy transfer dynamics in the organic dendrimers.