Three different classes of boron and nitrogen containing light metal complex hydrides have been investigated, resulting from the reactions of LiNH2 with LiBH4, NaNH2 with NaBH4 and MHx (where M = Li, Na and Ca) with NH3BH3. A rich variety of new phases has been identified, which exhibit modified decomposition pathways and onset temperatures of hydrogen desorption as low as 40°C. In each case the composition of phases formed has been examined in detail and the products of thermal decomposition—solid and gaseous—have been determined.