The adsorption, thermoreactions, and photoreactions of NO coadsorbed with K on Si(111)7×7 at 90 K have been studied and compared with the results obtained from the Kfree surface. The experiments were performed under ultra-high vacuum conditions using high resolution electron energy loss spectroscopy, work function change measurements, and mass spectrometry. NO adsorbs both molecularly and dissociatively on the K-free surface. Two molecular N–O stretching modes are observed at 188 and 225 meV. The concentration of these NO molecules on the surface decreases as the K exposure increases and vanishes at high K exposures. A new N–O stretching mode, attributed to adsorption of NO molecules on K clusters, is observed at 157 meV. After thermal heating or photon irradiation, the surface is covered with atomic O and N. The surface is more oxidized in the presence of K. A steady decrease in the photodesorption cross section is observed as the K exposure increases and is attributed to K-induced band structure changes.