This paper reports on hybrid, bioactive ceramic Ca-P-based coating formation on a Ti-6Al-7Nb alloy substrate to enhance the osseointegration process. The Ti alloy was anodized in a Ca3(PO4)2 suspension and then the additional layer was formed by the sol-gel technique to obtain a mixture of the calcium phosphate compounds. The oxide layer was porous and additional ceramic particles were formed after sol-gel treatment (scanning electron microscopy analysis coupled with energy-dispersive x-ray spectroscopy). The ceramic particles were formed on some parts of the oxide layer and did not completely fill the pores. The layer thickness of the anodized Ti alloy was comprised between 3.01 and 5.03 µm and increased to 7.52–12.30 µm after the formation of an additional layer. Post-treatment of the anodized Ti alloys caused a decrease in surface roughness, and the layer became strongly hydrophilic. Crystalline phase analysis (X-ray diffraction, XRD) showed that the hybrid layer was composed of TiO2 (anatase), Ca3(PO4)2, Ca10(PO4)6(OH)2 and a partially amorphous phase; thus, the layer was also analyzed by Raman spectroscopy. The hybrid layer showed worse adhesion to the substrate than the anodized layer only; however, the coating was not brittle, and the first delamination of the layer was determined at 1.84 ± 0.11 N during scratch-test measurement. The hybrid coating was favorable for collagen type I and lactoferrin adsorption, strongly influencing the proliferation of osteoblast-like MG-63 cells. The coatings were cytocompatible and may find applications in formation of the functional layers on long-term implants’ surface after.