The transformation of kaolinite to halloysite-7 Å was identified in the kaolin deposit of São Vicente de Pereira (SVP), using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Both the 02, 11̅ and 13̅, 13 reflections show changes in the XRD patterns along the kaolinite to halloysite-7 Å transition, and the FTIR spectra show changes corresponding to both OH− and Si–O–stretching bands and Al–O–Si–bending vibrations. The interlayer water content in the kaolinite structure increases during transition. The two-layer periodicity of well-ordered kaolinite and rolling up of kaolinite plates are observed using high-resolution transmission electron microscopy (HRTEM). Long and short tubes exhibit halloysite-7 Å. No structural Fe was found in the kaolinite samples. Analytical electron microscopy (AEM) indicates no substitution of Al3+ for Si4+. The Si/Al ratio shows values of ~1 for the kaolinite and rolled kaolinite plates. The 27Al magic angle spinning neutron magnetic resonance (MAS-NMR) spectra display a resonance centered at ~1 ppm, assigned to six-coordinated aluminum. The transformation of kaolinite to halloysite-7 Å is controlled by surface reaction.