Laser powder bed fusion (L-PBF) additive manufacturing (AM) is an effective method of fabricating nickel–titanium (NiTi) shape memory alloys (SMAs) with complex geometries, unique functional properties, and tailored material compositions. However, with the increase of Ni content in NiTi powder feedstock, the ability to produce high-quality parts is notably reduced due to the emergence of macroscopic defects such as warpage, elevated edge/corner, delamination, and excessive surface roughness. This study explores the printability of a nickel-rich NiTi powder, where printability refers to the ability to fabricate macro-defect-free parts. Specifically, single track experiments were first conducted to select key processing parameter settings for cubic specimen fabrication. Machine learning classification techniques were implemented to predict the printable space. The reliability of the predicted printable space was verified by further cubic specimens fabrication, and the relationship between processing parameters and potential macro-defect modes was investigated. Results indicated that laser power was critical to the printability of high Ni content NiTi powder. In the low laser power setting (P < 100 W), the printable space was relatively wider with delamination as the main macro-defect mode. In the sub-high laser power condition (100 W ≤ P ≤ 200 W), the printable space was narrowed to a low hatch spacing region with macro-defects of warpage, elevated edge/corner, and delamination happened at different scanning speeds and hatch spacing combinations. The rough surface defect emerged when further increasing the laser power (P > 200 W), leading to a further narrowed printable space.