TEM analysis of mesoporous materials is generally undertaken to give qualitative results. Accurate quantitative analysis is demonstrated in this study. A systematic image analysis of a powder form of a hexagonal mesoporous material known as KIT-6 is conducted using a transmission electron microscope (TEM). Three types of image contrast typically appear in this material (a hexagonal honeycomb structure, wide and narrow parallel lines). The honeycomb face is used to characterise this material in terms of a conventional 2-D hexagonal structure and the d-spacings for the (100) and (110) planes are experimentally measured in varying focus conditions. A tilting experiment is conducted to determine how the angle of tilt affects the line spacing and their visibility. Tilting has very little effect on the line spacing, whereas it affects the visibility of both the wide and narrow lines by limiting an angle range of visibility. The hexagonal lattice structure parameter determined by TEM method is found to be approximately 7% lower than that calculated by low-angle X-ray diffraction. Thus we conclude that TEM data can be used to determine the geometry and dimensions of hexagonal mesoporous silica materials, with a small error in the hexagonal lattice parameter.