This article examines the structural characteristics of four South African fly ashes and their structural changes with beta-cyclodextrin so as to compare their structural responses to fly ash-beta-cyclodextrin (FA-beta CD) composite. The four different fly ashes, obtained from different power stations in South Africa were subjected to x-ray fluorescence (XRF), particle size distribution, x-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analysis. FA-beta CD composites were subjected to XRD and FTIR analyses. The XRF analysis showed that all the fly ash samples used are in class F with SiO2+Al2O3+Fe2O3 greater than 70%. The average particle sizes of all fly ash samples were less than 0.075mm; the major mineral phase in all fly ash samples was quartz (SiO2). The FTIR analysis showed Si-O-Si asymmetric and Al-O symmetric stretching vibrations in all fly ash samples. FA-beta CD composites for all the fly ashes revealed additional upcoming peaks between diffraction angles (2 theta) 10 degrees and 25 degrees, which was not in the raw fly ashes. Shift in FTIR spectra frequencies and an additional peak at approximately 1155cm(-1) attributed to O-Si-O bending vibration were observed in all the composite samples.