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Sugarcane bagasse ash re-utilisation has been advocated as a silica-rich feed for zeolites, pozzolans in cements and concretes, and geopolymers. However, many papers report variable success with the incorporation of such materials in these products as the ash can be inconsistent in nature. Therefore, understanding what variables affect the ash quality in real mills and understanding the processes to characterise ashes is critical in predicting successful ash waste utilisation. This paper investigated sugarcane bagasse ash from three sugar mills (Northern NSW, Australia) where two are used for the co-generation of electricity. Data shows that the burn temperatures of the bagasse in the high-efficiency co-generation boilers are much higher than those reported at the temperature measuring points. Silica polymorph transitions indicate the high burn temperatures of ≈1550 °C, produces ash dominated α −quartz rather than expected α-cristobilite and amorphous silica; although α-cristobilite, and amorphous silica are present. Furthermore, burn temperatures must be ≤1700 °C, because of the absence of lechatelierite where silica fusing and globulisation dominates. Consequently, silica-mineralogy changes deactivate the bagasse ash by reducing silica solubility, thus making bagasse ash utilisation in synthetic zeolites, geopolymers, or a pozzolanic material in mortars and concretes more difficult. For the ashes investigated, use as a filler material in cements and concrete has the greatest potential. Reported mill boiler temperatures discrepancies and the physical characteristics of the ash, highlight the importance of accurate temperature monitoring at the combustion seat if bagasse ash quality is to be prioritised to ensure a usable final ash product.