We have systematically investigated Na adsorption on the [Formula presented] surface at room temperature using scanning tunneling microscopy (STM). Below the critical coverage of 0.08 monolayer, we find intriguing contrast modulation instead of localized Na adsorbates, coupled with streaky noise in the STM images, which is accompanied by monotonic work function drop. Above the critical coverage, Na clusters emerge and form a self-assembled array. Combined with first-principles theoretical simulations, we conclude that the Na atoms on the ([Formula presented]) surface are, while strongly bound ([Formula Presented]) to the surface, highly mobile in “basins” around the Si rest atoms, forming a two-dimensional gas phase at the initial coverage and that the cluster at the higher coverage consists of six Na atoms together with three Si adatoms. {\textcopyright} 2003 The American Physical Society.