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As-grown graphene via chemical vapor deposition (CVD) has potential defects, cracks, and disordered grain boundaries induced by the synthesis and transfer process. Graphene/silver nanowire/graphene (Gr/AgNW/Gr) sandwich composite has been proposed to overcome these drawbacks significantly as the AgNW network can provide extra connections on graphene layers to enhance the stiffness and electrical conductivity. However, the existing substrate (polyethylene terephthalate (PET), glass, silicon, and so on) for composite production limits its application and mechanics behavior study. In this work, a vacuum annealing method is proposed and validated to synthesize the free-stand Gr/AgNW/Gr nanocomposite film on transmission electron microscopy (TEM) grids. AgNW average spacing, optical transmittance, and electrical conductivity are characterized and correlated with different AgNW concentrations. Atomic force microscope (AFM) indentation on the free-stand composite indicates that the AgNW network can increase the composite film stiffness by approximately 460% with the AgNW concentration higher than 0.6 mg/mL. Raman spectroscopy shows the existence of a graphene layer and the disturbance of the AgNW network. The proposed method provides a robust way to synthesize free-stand Gr/AgNW/Gr nanocomposite and the characterization results can be utilized to optimize the nanocomposite design for future applications.