In the present work, we report a synthesis procedure for the preparation of vertically aligned mesoporous silica thin films containing long, nanometer-scale thin silver nanowires inside pores. The inter-channel nanowires had a fine crystalline structure and a diameter of no more than 2 nm. Despite the diameter being the edge of the theoretical possibility of synthesis, the nanowires were stable enough to be observed by transmission electron microscope and could be clearly observed. For the synthesis, we applied the idea of silica nanoreactors, and the procedure consists of two steps: fabrication of an initial organically-functionalized silica thin film containing silver ions distributed regularly inside vertically aligned pores and following thermal decomposition resulting in the decomposition of the organic anchoring groups and the formation of metallic crystalline nanowires from released silver atoms. Both the final nanocomposite and the initial material were studied by means of transition electron microscopy and electrochemical techniques: linear scan and differential pulse anodic stripping voltammetry. The crystallinity of silver nanowires inside silica mesopores was proved by electron diffraction. The spatial confinement realized by silica nanochannels facilitated the stabilization of relatively small and ultra-thin nanowires and the formation of a hexagonal P6 3 /mmc silver crystalline structure instead of the more common Fm3m cubic.