The results of XPS measurements (core levels and valence bands) of P⁺, Ca⁺, P⁺Ca⁺ and Ca⁺P⁺ ion implanted (E=30 keV, D=1×10¹⁷cm^-2) commercially pure titanium (cp-Ti) and first-principles density functional theory (DFT) calculations demonstrates formation of various structural defects in titanium dioxide films formed on the surface of implanted materials. We have found that for double implantation (Ti:P⁺,Ca⁺ and Ti:Ca⁺,P⁺) the outermost surface layer is formed mainly by Ca and P, respectively, i.e. the implantation sequence is very important. The DFT calculations show that under P⁺ and Ca⁺P⁺ ion implantation the formation energies for both cation (P-Ti) and anion (P-O) substitutions are comparable, which can induce the creation of [PO₄]^3- and Ti-P species. For Ca⁺ and P⁺Ca⁺ ion implantation the calculated formation energies correspond to Ca²⁺-Ti⁴⁺ cation substitution. This conclusion is in agreement with XPS Ca 2p and Ti 2p core levels and valence-band measurements and DFT calculations of the electronic structure of related compounds. The conversion of implanted ions to Ca²⁺ and [PO₄]^3- species provides a good biocompatibility of cp-Ti for further formation of hydroxyapatite.