Photoluminescence (PL) from surface-oxidized Si nanocrystals (nc-Si) was studied as a function of the size. The size of nc-Si was comparable with or larger than the Bohr radius of free excitons in bulk Si crystal (5 nm). In contrast to smaller surface-oxidized nc-Si (typically as small as a few nanometers in diameter), these relatively large nc-Si exhibited PL properties with strong size dependence. A high-energy shift of the PL peak from the vicinity of the bulk band gap to the visible region was observed. This PL shift was accompanied by a shortening of the PL lifetime and an increase in the exchange splitting energy of excitons. These size dependences indicate that the PL originates from the recombination of excitons confined in nc-Si. The differences in the PL properties between H-terminated and surface-oxidized nc-Si are also discussed.