An ideal vascular phantom should be anatomically accurate, have mechanical properties as close as possible to the tissue, and be sufficiently transparent for ease of visualization. However, materials that enable the convergence of these characteristics have remained elusive. We report the fabrication of patient‐specific vascular phantoms with high anatomical fidelity and optical transparency, and mechanical properties close to those of vascular tissue. These final properties were achieved by 3D‐printing patient‐specific vascular models with commercial elastomeric acrylic‐based resins before coating with thiol‐based photopolymerizable resins. Ternary thiol‐ene‐acrylate chemistry was found optimal. A PETMP/allyl glycerol ether (AGE)/polyethylene glycol diacrylate (PEGDA) coating with a 30/70% AGE/PEGDA ratio applied on a flexible resin yielded elastic modulus, UTS and elongation of 3.41 MPa, 1.76 MPa and 63.2%, respectively, in range with the human aortic wall. The PETMP/AGE/PEGDA coating doubled the optical transmission from 40% to 80%, approaching the 88% of the benchmark silicone‐based elastomer. Higher transparency correlates with a decrease in surface roughness from 2000 to 90 nm after coating. Coated 3D‐printed anatomical replicas are showcased for pre‐procedural planning and medical training with good radio‐opacity and echogenicity. Thiol‐click chemistry coatings, as a surface treatment for elastomeric stereolithographic 3D‐printed objects, address inherent limitations of photopolymer‐based additive manufacturing.This article is protected by copyright. All rights reserved