This study focuses on the comparative evaluation of star (branched) and linear poly(l,d-lactic acid) (PDLLA) as degradable materials employed in controlled release. The polymers were prepared via ring-opening polymerization initiated by decanol (linear), pentaerythritol (4-armed star) and dipentaerythritol (6-armed star), and processed both in the form of films and nanoparticles. Independent of the length or number of their arms, star polymers degrade slower than linear polymers, possibly through a surface (vs bulk) mechanism. Further, the release of a model drug (atorvastatin) followed zero-order-like kinetics for the branched polymers, and first-order kinetics for linear PDLLA. Using NHOst osteoblastic cells, both linear and star polymers were devoid of any significant toxicity and released atorvastatin in a bioavailable form; cell adhesion was considerably lower on star polymer films, and the slower release from their nanoparticles appeared to be beneficial to avoid atorvastatin overdosing.