The invention provides a three-dimensional flower-like nano composite material as well as a preparation method and application thereof, the composite material is NiO/PDDA-RGO, and the material is prepared from PDDA-RGO and synthesized NiO by hydrothermal reaction and calcining via an ultrasonic-assisted method. Reduced graphene oxide in the composite material is used as a NiO carrier, so that theproblem of low NiO conductivity is solved, the adsorption characteristic of an analyte is improved to enhance the electrochemical performance, and the composite material is an excellent electrode modification material. The NiO/PDDA-RGO composite material is modified on the surface of an electrode to construct electrochemical sensing for enzyme-free nitrite detection. According to the method, thetechnical problems of long recognition time, complexity, high cost, low sensitivity, unobvious recognition effect and the like in the prior art are solved, high-sensitivity and high-selectivity detection for nitrite in a complex environment can be realized, and the composite material has a very good application prospect in the analysis fields of environments, foods and the like.