Laser desorption/ionization techniques, such as matrix-assisted laser desorption/ionization (MALDI) and surface-assisted laser desorption/ionization (SALDI), are the basis of modern mass spectrometry, enabling the analysis of a wide range of chemical compounds, from small molecules to biopolymers. MALDI uses organic matrices to support ionization, while SALDI relies on inorganic surfaces or nanomaterials, which reduce background and improve measurement sensitivity. This review focuses on the potential of using silver nanoparticles (AgNPs) in LDI-MS, with particular emphasis on their synthesis from the gas phase (CVD, Chemical Vapor Deposition). The key role of nanostructures in increasing ionization efficiency and analytical selectivity is emphasized. The CVD technique enables precise control over the morphology, size, and distribution of nanoparticles, which translates into better repeatability and sensitivity of nanostructure-assisted laser desorption/ionization mass spectrometry (NALDI-MS) measurements. The latest achievements in this field are presented, as well as potential applications of CVD-produced AgNPs in analytical chemistry, environmental analysis, and the petrochemical industry.