The aim of this study is to observe the effect of process parameters on residual stresses and relative density of Ti6Al4V samples produced by Selective Laser Melting. The investigated parameters were hatch laser power, hatch laser velocity, border laser velocity, high-temperature preheating and time delay. Residual stresses were evaluated by the bridge curvature method and relative density by the optical method. The effect of the observed process parameters was estimated by the design of experiment and surface response methods. It was found that for an effective residual stress reduction, the high preheating temperature was the most significant parameter. High preheating temperature also increased the relative density but caused changes in the chemical composition of Ti6Al4V unmelted powder. Chemical analysis proved that after one build job with high preheating temperature, oxygen and hydrogen content exceeded the ASTM B348 limits for Grade 5 titanium.