Room-temperature ultra-high vacuum (UHV) scanning tunnelling microscopy (STM) has been employed to investigate free radical chemistry on the Si(111)-7 × 7 surface with atomic-scale spatial resolution. In particular, due to its single-site binding mechanism and extensive previous study on the Si(100)-2 × 1 surface, the nitroxyl free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was explored. UHV STM imaging of isolated molecules revealed that TEMPO covalently reacts with adatom dangling bonds with high affinity. By monitoring TEMPO adsorption as a function of surface coverage, TEMPO was also found to preferentially bind to centre adatom sites at the initial stages of adsorption. On the other hand, as the surface coverage increased, TEMPO molecules adsorbed to centre adatoms and corner adatoms approached a ratio of 1:1. At all surface coverage levels, TEMPO showed minimal preference for binding to either the faulted or unfaulted half of the unit cell. Consequently, upon saturation, the TEMPO adlayer exhibited long-range ordering and preserved the underlying 7 × 7 surface reconstruction. This study provides fundamental insight into free radical surface chemistry and suggests a direct pathway for forming nearly perfectly ordered organic adlayers on the Si(111)-7 × 7 surface.