Several new photosensitive, yet mechanical insensitive energetic coordination hybrid crystals (ECHCs) containing nano-sheets of carbohydrazide functionalized graphene oxide (GO-CHZ), as a doping agent, were prepared and comprehensively characterized. It has been demonstrated that the transition metal centers in ECHCs are 6-coordinated with the GO-CHZ and CHZ as coligands. The SEM analyses show that the GO-CHZ-CuN-1 ECHC has irregular shapes, while its cobalt and nickel analogues are homogeneous crystalline embedded with layered GO-CHZ nano-sheets. Powder X-ray diffraction study indicates that the type of metals and doping of GOCHZ would not change the space group and symmetry of the crystals of ECHCs. The doping of CHZ-CoP and CHZNiP by GO-CHZ significantly improves their impact sensitivity (from 1.0 J to over 10 J). Notably, by using GOCHZ as a doping agent, the ignition delay of CHZ-CoP was also greatly improved (only 214 mu s for GO-CHZ-CoP-3), which is much shorter than that of pristine CHZ-CoP (401 mu s), even though the latter used a laser with 30 times higher energy density. It indicates that these new materials are highly attractive for future smart laserignition systems.