An efficient and useful synthetic route for the synthesis of linear and star polystyrenes (PS) is described, employing living anionic polymerization to link living polystyryl anions to inexpensive and readily available malonyl chloride and other coupling agents with higher functionality that were generated in situ at room temperature. The polymers prepared in this way were analyzed and characterized by size-exclusion chromatography (SEC), temperature gradient interaction chromatography (TGIC) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). It was observed that with the increase in molecular weight of the living PS, the number of arms and weight fraction of higher arm polymers decrease significantly.