Additive manufacturing (AM) of hot-work tool steels such as H13 offers unique opportunities for producing complex, conformally cooled tools with reduced production time and material waste. In this study, five metal AM technologies—Fused Deposition Modeling and Sintering (FDMS, Desktop Metal Studio System and Zetamix), Binder Jetting (BJ), Laser Powder Bed Fusion (LPBF), and Directed Energy Deposition (DED)—were compared in terms of microstructure, porosity, and post-processing heat treatment response. The as-printed microstructures revealed distinct differences among the technologies: FDMS and BJ exhibited high porosity (6–9%), whereas LPBF and DED achieved near-full densification (<0.1%). Samples with sufficiently low porosity (BJ, LPBF, DED) were subjected to tempering and quenching treatments to evaluate hardness evolution and microstructural transformations. The satisfactory post-treatment hardness was observed in both tempered and quenched and tempered BJ samples, associated with secondary carbide precipitation, while LPBF and DED samples retained stable martensitic structures with hardness around 600 HV0.5. Microstructural analyses confirmed the dependence of phase morphology and carbide distribution on the thermal history intrinsic to each AM process. The study demonstrates that while FDMS and BJ are more accessible and cost-effective for low-density prototypes, LPBF and DED offer superior density and mechanical integrity suitable for functional tooling applications.