The determination of kaolinite order-disorder by X-ray diffraction is problematic due to overlapping peaks from associated kaolin minerals and X-ray amorphous phases. This paper presents a new index (Aparicio-Gala´n-Ferrell index — AGFI), measured on 02l and 11l reflections after decomposing individual peaks in the complex diffraction band in an effort to reduce interferences. The new index was tested with three kaolins, of varying structural order, and their admixtures containing different percentages of quartz, feldspar, illite, smectite, chlorite, halloysite and Fe hydroxides and silica gels. The AGFI is highly correlated with the percentage of low-defect kaolinite and the Hinckley Index. It is not as prone to interference by associated minerals and X-ray amorphous phases as other indices. The AGFI can be used to determine kaolinite order-disorder in a wide variety of kaolins and kaolinitic rocks; the only prerequisite is that the kaolinite content should be >10 wt.% in order for the results to be reproducible.