Phytic acid (IP6) and its salts are promising reagents to alleviate corrosion of metals, which are environmentally friendly and highly efficient, compared to some traditional inhibitors toxic to environment. This paper reports the studies of the structure and anticorrosion features of two kinds of the self-assembled monolayers (SAMs) Of IP6 at the silver surface under various pH values, 1.27 and 13, by using electrochemical and surface enhanced Raman scattering (SERS) spectroelectrochemical measurements. On the basis of recorded ex situ SERS spectra, different adsorption modes of both resulted SAMs of IP6 at the silver surfaces have been postulated. In addition, based on in situ SERS electrochemical measurements, a tentative explanation for the difference in corrosion potentials of two kinds of the silver surfaces in the presence of SAMs formed from completely protonated or deprotonated IP6 molecules has also been presented.