The formation of different nickel and cobalt layered hydroxide phases by a variety of solution and solid-state synthesis methods has been investigated. Initially, preparative methods were refined to generate single-phase products from metal(II) nitrate hexahydrate starting materials which were then characterised by powder X-ray diffraction, vibrational spectroscopy and thermogravimetric analysis. As well as the brucite type β-M(OH)2 and the hydrotalcite-like [M(OH)2-x(H2O)x]x+ alpha-phases (where M = Ni, Co), two different hydroxynitrate phases were isolated with the generic formula M(OH)2-x(NO3)x with x = 0.67 and 1.0 (where M = Ni, Co). The reduction of symmetry of the nitrate anion from D3h to C2v allows the alpha-phases to be distinguished from the two different layered hydroxynitrate phases by both infrared and Raman spectroscopy through the loss of symmetry and concomitant splitting of the degenerate bands. The symmetric N-O stretch enables the two hydroxynitrate phases to be distinguished from one another through the sharp absorption bands at ca. 1000 cm-1 (x = 0.67) and ca. 1050 cm-1 (x = 1.0). The thermogravimetric analysis data of the phases showed key differences between the layered hydroxides, with anhydrous phases having singular weight losses over short temperature ranges and hydrated phases having multiple losses over more extended temperature ranges.