Crystalline germanium was ablated with light at 532 nm from a frequency-doubled neodymium: yttrium aluminum garnet laser, and the resultant plume reacted with NO before deposition onto a substrate at 13 K. Lines in group A at 1543.8 and 3059.7 cm-1 that become enhanced at the initial stage of irradiation at 308 or 193 nm and also after annealing are attributed to ν1 and 2 ν1 of GeNO. Lines in group B at 1645.5 and 1482.8 cm-1 that become diminished after further irradiation of the matrix at 308 or 193 nm but become enhanced after annealing are attributed to symmetric NO stretch (ν1) and antisymmetric NO stretch (ν7) of ONGeNO. The assignments were derived based on wave numbers and isotopic ratios observed in the experiments with N15 - and O18 -isotopic substitutions and predicted with quantum-chemical calculations. Quantum-chemical calculations with density-functional theories (B3LYP and BLYP/aug-cc-pVTZ) predict four stable isomers of GeNO, six isomers of Ge2 NO, and four isomers of Ge (NO)2, with linear GeNO, cyc-GeNGeO, and cyc-GeONNO having the least energies, respectively. The formation mechanisms of GeNO and ONGeNO are discussed. In addition, a weak line at 1417.0 cm-1 and two additional lines associated with minor matrix sites at 1423.0 and 1420.3 cm-1 are assigned to GeN O-.