The paramagnetic resonance of Na5AlF2(PO4)2 single crystals with chromium impurity was studied. The Cr3+ centers have been found to replace the triclinic Al3+ positions. In the local coordinate system, the spectra of these centers were described by the spin Hamiltonian of rhombic symmetry. In addition, vanadium centers and unidentified triclinic symmetry centers have been observed.