The Hizeh-Jan kaolin deposit (northwest of Varzeghan, East-Azarbaidjan Province, NW Iran) is a product of the alteration of Eocene andesitic rocks. Based on mineralogical examinations, kaolinite, quartz, smectite, pyrophyllite, muscovite-illite, alunite, calcite, diaspore, goethite and hematite are the most abundant mineral phases in this deposit. The geochemical indicators, such as Y/Ho and Zr/Hf, indicate the non-CHARAC (non-Charge-radius control) behavior of these pairs, which are likely to be due to the occurrence of the tetrad effect phenomenon in this deposit. Simultaneous concave and convex shapes in the chondrite-normalized REE distribution patterns are a remarkable feature of the kaolin samples. Bivariate diagrams of the size of the third tetrad effect (T3) versus geochemical parameters such as Y/Ho, Nb/Ta and Zr/Hf ratios display two distinct populations for the kaolin samples. The first population is characterized by high T3 values (>0.13), which are near or on the fault zone. The second population is characterized by low T3 values (<0.13), and are farther from the fault zone. The obtained results from the geochemical data have furnished compelling evidence that fluid-rock interaction, overprint of hypogene processes by supergene ones, and structural control, are key controlling factors for the occurrence of tetrad effects in REE distribution patterns in the Hizeh-Jan kaolin deposit.