Highly oriented crystalline gold nanoislands (NIs) are self-assembled on MgO(001) substrates by pulsed laser deposition. Morphologies of the gold NIs are significantly dependent on the substrate temperature during gold deposition. Symmetrical-shaped NIs with Au(111) orientation are existence parallel to the MgO(001) substrate at low temperatures deposition (350 and 550 °C), while square-shaped and hexagonal-shaped gold NIs are co-existence whose crystallinity was Au(001) and Au(111), respectively. Extinction spectra of the gold NIs on MgO(001) substrates show that wide-range of photo-energy is disappeared. For a simple and useful plasmonic device, the produced gold NIs on MgO(001) substrates are applied to the surface-enhanced Raman scattering (SERS) chips. The SERS properties of the chips are evaluated using 4-MBA as a model analyte. From the SERS signal of a 4-MBA ring breathing mode, we obtain a significant enhancement factor over 107, which is approximately 10 times higher than that of a conventional SERS chip.