Polymer thermosets and composites based on rigid trizaine-trione (TATO) alkene and thiol monomers show great promise as bone fixation materials and dental composites due to their ability to efficiently crosslink via thiol-ene coupling chemistry into stiff and strong materials. In order to broaden the scope of these materials, a TATO thermoset was optimized for sterolithography (SLA) 3D printing through the addition of either a diluent (PETMP) and photo-absorber (Sudan I), or the addition of a free radical inhibitor (pyrogallol). A 3D printable hydroxyapatite (HA) composite was also formulated by adding a combination of nano-HA and micro-HA particles, which were found to increase the thermal stability and modulus of the material, respectively. The modulus of the printed thermosets containing Sudan I and pyrogallol exceeded any previously published acrylate-free thiol-ene SLA resins, at 1.6 (0.1) and 1.85 (0.06) GPa, respectively. The printed HA composite formulation had a modulus of 2.4 (0.2) GPa. All three formulations showed a comparable resolution to a commercially available SLA resin and were non-toxic toward Raw 264.7 and human dermal fibroblast cells. These results demonstrate the potential of TATO based SLA resins for the construction of strong, fully-customizable, printed implants for biomedical applications.