Two novel three-dimensional chiral metal phosphite open frameworks with 4-connected quartz topology, [Me-2-DABCO][M-2(HPO3)(3)] [M = Co (1), Zn (2); Me-2-DABCO = N,N'-dimethyl-1,4-diazabicyclo[2.2.2]octane] have been ionothermally synthesized in deep eutectic solvents (choline chloride/1,3-dimethylurea). It is interesting that the organic template, Me-2-DABCO, is in situ generated from the alkylation reaction of 1,4-diazabicyclo[2.2.2]octane and dimethyl phosphites.