Micro-energetic devices with energetic and functional diversity have attracted interest from scientific communities, through features such as the integration of energetic materials into micro-electro-mechanical systems (MEMS). In this study, a method for the preparation of nickel picrate energetic films on the sidewalls of a silicon microchannel plate (Si-MCP) is presented. The Si-MCP was produced by a photoelectrochemical process and a thin film of nickel (Ni) was synthesized by electroless plating of Ni on the sidewalls of the Si-MCP. The thin film of nickel picrate was successfully produced via an in situ chemical reaction method by introducing picric acid into the 3D ordered nickel/silicon microchannel plate (Ni/Si-MCP). Field emission scanning electron microscopy, Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy were used to study the morphological and structural properties of the thin film. The results demonstrate that picric acid reacted with Ni to form a nickel picrate thin film. Also, differential scanning calorimetry and thermogravimetric analysis were employed to characterize the thermal decomposition of the energetic film. The approach can solve the problem of integrating organic energetic materials with MEMS devices. Also, nickel picrate can release a mass of energy and gas simultaneously, which further enhances the functional diversity of MEMS devices.