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In this paper, selective laser sintering (SLS) was applied to join two materials by printing Ti–6Al–4V powder on a Ti substrate without any support parts. The characteristics of the interface between the as-built Ti–6Al–4V sample and the substrate were investigated. The analysis indicates that a heat-affected zone (HAZ) and the fish-scale type were formed at the joining area. The combination of smaller grains, acicular α′ martensite, and lamellar (α + β) structures was observed inside the interface zone. The hardness value at the interface area was measured by about 320 HV which is higher than 280 HV of the substrate and smaller than 369 HV of the as-built sample. The results predict that the SLS process is a promising method for manufacturing of hybrid materials.