Schiff’s base complexes bis(2-hydroxyacetophenoimine)nickel(II) [Ni(ohapim)2] and bis(2-hydroxyacetophenoimine)copper(II) [Cu(ohapim)2] were synthesized and studied for their idealist novel vapour source for chemical vapour deposition (CVD) application. Molecular structure was determined using single crystal X-ray diffraction, FT-IR, and elemental (C, H, N, and O) studies. Upon screening these complexes by dynamic thermogravimetric (TG) analyses, [Ni(ohapim)2] was found to be completely volatile and suitable for Ni/NiO CVD application. The temperature-dependent vapour pressure of [Ni(ohapim)2] was measured by using a transpiration apparatus and gave a value of 77.4 ± 0.8 kJ/mol for the enthalpy of sublimation (ΔH°sub) in the temperature range 527.86–584.22 K.