Poly(propylene fumarate) star polymers photochemically 3D printed with degradable thiol cross-linkers yielded highly tunable biodegradable polymeric materials. Tailoring the alkene:thiol ratio (5:1, 10:1, 20:1 and 30:1) and thus the cross-link density within the PPF star systems yielded a wide variation of both the mechanical and degradation properties of the printed materials. Fundamental trends were established between the polymer network cross-link density, glass transition temperature, and tensile and thermomechanical properties of the materials. The tensile properties of the PPF star-based systems were compared to commercial state-of-the-art non-degradable polymer resins. The thiolene-cross-linked materials are fully degradable and possess properties over a wide range of mechanical properties relevant to regenerative medicine applications.