AbstractStar‐shaped 1‐vinyl‐2‐pyrrolidone (VP)‐based polymers having four pendant arms were produced via high‐pressure RAFT using the trithiocarbonate‐functionalized core. The use of compression (p = 250 MPa) significantly reduced or eliminated star‐star/star‐chain coupling side reactions and termination process characteristics the for “core‐first” R‐type approach, still allowing for a “pseudo‐living” reaction course up to very high monomer conversion (>98%). Consequently, tailored and highly living star‐shaped poly(1‐vinyl‐2‐pyrrolidone)s (PVP) in a wide range of molecular weights M n = 2.0–175.6 kg/mol (Đ = 1.18–1.80) have been obtained. The chain extension of the produced polymer was carried out with methyl methacrylate (MMA) via photo‐induced RAFT (λ = 365 nm) in the presence of tertiary amine catalyst, yielding well‐defined amphiphilic star‐shaped block copolymers. DSC measurements showed that synthesized star‐shaped PVP homopolymers revealed much lower glass transition temperature values compared to their commercially supplied linear analogs.