Optoelectronic properties of Si nanocrystals (SiNCs) were studied by combining scanning tunneling spectroscopy (STS) and optical measurements. The photoluminescence (PL) of phenylacetylene functionalized SiNCs red shifts relative to hexyl- and phenyl-capped counterparts, whereas the absorption spectra and the band gaps extracted from STS are similar for all surface groups. However, an in-gap state near the conduction band edge was detected by STS only for the phenylacetylene terminated SiNCs, which can account for the PL shift via relaxation across this state.