Sequential anionic polymerization of styrene and divinylbenzene (DVB) is known to lead to the formation of star-shaped polymers. This ’arms-first’ method has been widely used and studied. It is known that this polymerization forms stars with anionically active cores. This article is concerned with the attempt to make asymmetric-star polymers utilizing these living carbanionic sites present in the core to form a second set of shorter arms growing out from the star core. The presence of remaining unreacted DVB within the core was found to cause the stars to couple to form linked double stars and other larger structures. Results from detailed dilute solution studies of the resulting polymers are reported. It was found that the results obtained from size exclusion chromatography for the double stars were flow rate dependent; only at low flow rates was a true size separation obtained.