The titanium scaffolds and surface-porous implants are manufactured by fast and cheap additive methods such as selective laser melting (SLM). The obtained irregularity and relative biological inertness of the titanium need proper surface modification. This research is aimed at forming bioactive multicomponent oxide coatings by micro-arc oxidation (MAO) at different process parameters on the selective laser-melted Ti13Zr13Nb alloy. The MAO process was carried out in a base solution containing 0.15 mol/L Ca and 0.1 mol/L GP, with different amounts of metasilicate added under two different applied voltages. Scanning electron microscopy, atomic force microscopy, X-ray electron diffraction spectroscopy, nanomechanical and nano scratch tests, water contact angle measurements, phosphate deposition observed in long-term immersion tests, and biological LDH and MTT assays were performed. The results showed that the coating microstructure, morphology, and properties were significantly dependent on process parameters. In particular, the metasilicate addition and its rising content in the electrolyte resulted in the higher development of the surface followed by better viability of osteoblasts at no necrosis, with no negative change in the other parameters, usually close to those obtained on silicon-free coatings. The obtained results prove that the addition of silicon to the electrolyte at the partial expense of calcium can be favorable for long-term titanium implants made by selective laser melting.