A sample of 304L stainless steel manufactured by Laser Engineered Net Shaping (LENS) was characterized in 3D using TriBeam tomography. The crystallographic, structural, and chemical properties of the as-deposited microstructure have been studied in detail. 3D characterization reveals complex grain morphologies and large orientation gradients, in excess of 10∘, that are not easily interpreted from 2D cross-sections alone. Misorientations were calculated via a methodology that locates the initial location and orientation of grains that grow during the build process. For larger grains, misorientation increased along the direction of solidification. For grains with complex morphologies, K-means clustering in orientation space is demonstrated as a useful approach for determining the initial growth orientation. The gradients in misorientation directly tracked with gradients in chemistry predicted by a Scheil analysis. The accumulation of misorientation is linked to the solutal and thermal solidification path, offering potential design pathways for novel alloys more suited for additive manufacturing.