Twenty two new complexes of some tervalent metals (aluminum, chromium, iron, and lanthanides) with nitrozohydroxylamine N-alkyl(benzyl) derivatives · nH 2 O, (m = 1-5) were synthesized and isolated in a crystalline state. The crystal and molecular structures of the iron(III) complex with N-(2-fluorobenzyl)-N-nitrozohydroxylamine were determined by X-ray diffraction. An octahedral coordination of the central ion and a bidentate chelating coordination of the organic ligand were established. The spectral criteria of coordination of nitrozohydroxylamine alkyl(benzyl) derivatives were determined, and the complexation processes in solutions were studied.The compounds containing N-nitrozohydroxylamine moieties are good chelating reagents able of forming stable metal complexes with metals of various types. They are widely used in chemistry as analytical reagents for the extraction of many metals [1][2][3][4][5][6][7][8][9][10][11][12][13][14] and their spectrophotometric analysis [15], and as precursors for the synthesis of nanoparticles of metal oxides [16][17][18][19][20].