We report on transport measurement performed on a room-temperature-operating ultra-small Coulomb blockade devices with a silicon island of sub-5nm. The charge stability at 300K exhibits a substantial change in slopes and diagonal size of each successive Coulomb diamond, but remarkably its main feature persists even at low temperature down to 5.3K except for additional Coulomb peak splitting. This key feature of charge stability with additional fine structures of Coulomb peaks are successfully modeled by including the interplay between Coulomb interaction, valley splitting, and strong quantum confinement, which leads to several low-energy many-body excited states for each dot occupancy. These excited states become enhanced in the sub-5nm ultra-small scale and persist even at 300K in the form of cluster, leading to the substantial modulation of charge stability.