The observation of (111) Si/SiO2interfacePb0defects (modeled as0Si≡Si3) with dangling bonds positioned along [11¯1], [1¯11], and [111¯] from low‐temperature (T≲30 K) electron spin resonance measurements is reported. This is connected with the particular structure (SiOx) of the attendant very near‐Si interfacial transition region for the oxidation method invoked. Some instructive information as to the precise atomic modeling of the Si/SiO2interface is inferred.