Three-dimensional printing (3DP) has been employed to fabricate scaffolds with advantages of fully controlled geometries and reproducibility. In this study, the scaffold structure design was established through investigating the minimum feature size and powder size distribution. It was then fabricated from the 3DP plaster-based powders (CaSO4·1/2H2O). Scaffolds produced from this material demonstrated low mechanical properties and a rapid degradation rate. This study investigated the effects of heat treatment on the mechanical and in vitro degradation properties of the CaSO4 scaffolds. The occurrence of dehydration during the heating cycle offered moderate improvements in the mechanical and degradation properties. By using a heat treatment protocol of 200°C for 30 min, compressive strength increased from 0.36 ± 0.13 MPa (pre-heat-treated) to 2.49 ± 0.42 MPa (heat-treated). Heat-treated scaffolds retained their structure and compressive properties for up to two days in a tris-buffered solution, while untreated scaffolds completely disintegrated within a few minutes. Despite the moderate improvements observed in this study, the heat-treated CaSO4 scaffolds did not demonstrate mechanical and degradation properties commensurate with the requirements for bone-tissue-engineering applications.