This study reports the mineralogical characterization of kaolin occurrences in the State of Rio de Janeiro, Brazil, to identify new kaolinite and halloysite deposits. Samples were collected in 10 pegmatites with varying sizes for X-ray diffractometry, chemical analysis by X-ray fluorescence, and scanning electron microscopy studies. The results indicated that the kaolin occurrences were of weathered origin, wherein some places there were occurrences of tubular halloysite. Concerning the regolith stratigraphy, samples located in the saprock zone were found to contain kaolinite and/or halloysite contents from 0 to 10.1%, while those located in the saprolite zone contained kaolinite and/or halloysite contents from 16.3% to 34.9%. Kaolinite and/or halloysite-7Å were formed from plagioclase weathering instead of K-feldspar or mica, and the halloysite-7Å occurrence was related to samples in regions with a higher degree of weathering.