We report an integrated experimental and theoretical study of the two-dimensional polar selenogermanate compound Na2Ge2Se5, which exhibits strong nonlinear optical (NLO) second harmonic generation response in the visible and infrared region. The compound is type-I phase-matchable with a large SHG coefficient chi((2))approximate to 5290 pm V-1, which is the second highest among the phase-matchable NLO materials. It also performs as an NLO frequency mixer to produce radiation via difference frequency generation. The compound is optically transparent from the visible (0.521 mu m) to the far IR (18.2 mu m) and melts congruently. Ab initio density functional theory band structure calculations show that the unusually large second-order optical nonlinearity is attributed to the two-dimensional character of the crystal structure. Raman, IR and optical absorption spectroscopy, differential thermal analysis, NLO properties of derivatives of Na2Ge2Se4.55Te0.45 and Na2Ge1.64Sn0.36Se5 and thermal expansion behavior studies are also reported. (C) 2012 Elsevier Inc. All rights reserved.