The M-phase solid solutions Li1+x−yNb1−x−3yTix+4yO3) (0.1 ≤ x ≤ 0.3, 0 ≤ y ≤ 0.175) in the Li2O–Nb2O5–TiO2 system have promising microwave dielectric properties. However, these compounds can contain small quantities of ferroelectric impurities that affect the polarization response of the material. Due to their low concentration and their chemical similarity to the host material, the impurities cannot be detected by x-ray diffraction or local elemental analysis. Scanning surface potential microscopy and piezoresponse imaging were used to analyze phase compositions in this system. Piezoresponse imaging demonstrated the presence of thin (<200–300 nm) ferroelectric layers on the grain boundaries oriented along the c-axis of the M-phase. Differences between the surface potential and the piezoresponse of ferroelectric multicomponent systems are discussed.