In this article, a surface‐enhanced Raman scattering (SERS) substrate of silver nanocap arrays was reported. With increasing the size of nanocaps, the localized surface plasmon resonance (LSPR) of the arrays exhibited tunable ability in the visible spectral region. The optical response of the nanocap arrays stimulated their use in SERS experiments. The assessment of SERS activity of the nanocap arrays was performed by using the 514.5 nm excitation line, and different average enhancement factor (EF) values were obtained. The good tunability of LSPR, relatively high average EF values and long‐range order of these substrates suggest that the silver nanocap arrays have promising applications as functional components in spectroscopy, immunoassay, biosensors, and biochips.