Li_0.28Na_1.72Ge₄O₉:Cr (0.1mol.%) and Li_0.28Na_1.72Ge₄O₉:Cr, Mn (0.1mol%, 0.1mol.%)  (LNG) single crystals have been prepared by Czochralski method. They were investigated by electron paramagnetic resonance (EPR) and photoluminescence (PL)  in a temperature range of 3-300 K. EPR signal from Cr³⁺ ions shows at least two magnetically nonequivalent centers and some features characteristic of dissimilar ion pairs transitions (chromium and sodium), that are found from roadmap at high magnetic fields (over 4000 Gs) in limited range of angles. Manganese ion enters as divalent ion and reveals different locations. The area in roadmap where dissimilar pairs transitions are located is split in a case of Mn codoped crystal. 

PL spectra show two bands centered at about 425 nm and 695 nm, which are attributable to chromium ions in disordered matrices. Co-doping with Mn²⁺ leads to energy transfer to chromium ions. The maximum of PL for LNG:Cr, Mn is about 20 times higher than that for chromium only doped crystal.

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