Celsian with a chemical composition of Ba0.75Sr0.25Al2Si2O8, is synthesized by using coal fly ash (byproduct of a Mexican coal-burning power plant, composed mainly by SiO2 and Al2O3) as main raw material. The thermal behavior of the synthesized material is evaluated by differential (DTA) and gravimetric (TGA) thermal analyses as well as by heating microscopy; its coefficient of linear thermal expansion (CTE) is also determined. Heating microscopy shows that cylinders of compacted powdered Celsian start sintering at ∼1140 ºC, which is associated with a considerable contraction occurring up to 1500 ºC. The mean CTE value of the material in the temperature range of 30-1100ºC is slightly affected by the synthesis conditions employed. Synthesis at 1400 or 1300 ºC during 10 h, with a pre-calcination step at 900 ºC/5h in both cases, produce mean CTE values of 5.15 x 10-6 and 5.43 x 10-6 ºC-1, respectively. On the other hand, Celsian synthesized at 1400 ºC/10 h, without the pre-calcination step, has a mean CTE value of 5.25 x 10-6 ºC-1. Lastly, the DTA/TGA analysis of the synthesized material shows that a slight weight gain takes place from room temperature to 1100ºC, which is followed by a slight weight loss up to 1300ºC. This is attributed to oxidation and evaporation of some of the impurities present in the material.