In this paper we give new results on the physical gelation of a tactic polystyrene-carbon disulfide (CS2) solutions in relation to the structure of the chains. We demonstrate here the starlike effect on the onset of gelation supported by well-improved techniques such as the ball-drop method, differential scanning calorimetry, measurements of the static modulus, and oscillatory rheometry. The sol-gel phase diagrams show that the increase of the degree of branching has a noticeable impact on gel formation but with approximately constant melting enthalpy. The chemical junctions between branches in the star molecules result in an increase of the gelation temperature with respect to linear chains of equal concentration and overall molecular weight and in a decrease in the gel modulus at a given concentration.