The retention behavior of star-shaped polystyrene (PS) at the liquid chromatographic critical condition of linear PS was investigated. The star-shaped PS samples were prepared by anionic polymerization of styrene and subsequent linking of the polystyryl anions with divinylbenzene. The linking reaction yields a series of star-shaped PS with different number of branches of equal length. Three star-shaped PS samples with different arm molecular weight (MW) were prepared. To investigate the MW (hence the branch number) dependence of the LCCC (liquid chromatography at the critical condition) retention, the two-dimensional liquid chromatography method was used-first separating the polymers with respect to the molecular weight and subsequently separating the effluent by LCCC. Two different pore size columns were used for the LCCC separation to investigate the pore size dependence. The LCCC retention shows a very complex behavior. The retention time of the star-shaped PS shows a strong variation with MW (branch number) at the coelution condition of linear PS, and the deviation from the coelution behavior is more serious at a smaller pore sized column. The peculiar LCCC retention behavior was successfully delineated by a lattice Monte Carlo method taking into account the excluded volume and weak attractive interaction of the chain ends.