Natural dyes generally fan into two categories; organic dyes coming from animals and plants and inorganic dyes obtained from various minerals such as bengala, loess, ultramarine, prussian blue and etc. The main components of volcanic ash is clay mineral such as kaolinite, illite, quartz. Clay minerals Composing volcanic ash are kaolinite［$Al_4Si_4O_{10}{(OH)_{8}}$］, illite［$K_{X}Al_2(Si,;Al)_4O_{10}{(OH)}_2$］, quartz［$SiO_2$］, homblende［$Na_{0-1};Ca_2{(Mg,;Fe,;Al)}_5{(Si,;Al)}_{8}O_{22}{(OH)}_2$］and etc. And the redish color mainly comes from iron oxide. In this paper, two different classes of dyeing process were tested; dyeing with volcanic ash only and cationic agent pre-treatment followed by dyeing with volcanic ash. The compositions of the volcanic ash powder and the volcanic ash deposited on the cotton knitted fabrics identified by energy dispersive spectrometer and XRD analysis. The major chemical components of volcanic ash deposited on the cotton knitted fabrics were confirmed to be the saicon oxide, iron oxide, and aluminum oxide and etc. According to the analysis by XRD and EDS-SEM, kaolinite, illite and quartz were also identified.