We measured tip-enhanced Raman scattering (TERS) and photoluminescence (PL) spectra of benzenethiol-modified gold nanoplates fixed on graphite, by using a gold tip for scanning tunneling microscopy (STM) measurements. With increasing bias voltage between the tip and the nanoplates, the Raman intensities of benzenethiol gradually decreased, while the PL intensities decreased first and then increased. This implied that relatively low bias voltages are suitable for STM-TERS measurements. Both PL mapping and STM images of the nanoplates were simultaneously obtained. The PL mapping images showed that field enhancement by gap-mode plasmons between the tip and the nanoplates depended on their configuration.