The quest for smart and cost-effective demulsification materials to separate water-in-crude oil (W/O) emulsions is highly desired in the petroleum industry. In this paper, an assessment study was conducted on the potency of coal fly ash (CFA) as a demulsifier for W/O emulsions. To our knowledge, this is the first study reporting CFA as a demulsifier for highly stable W/O emulsions. W/O emulsion samples were prepared without using any conventional emulsifier. Asphaltenes in the crude oil acted as an emulsifier and stable emulsions were produced. Six W/O emulsion samples of the same crude oil to water volume ratio (4:6) were formulated. A reference sample was selected for comparison during demulsificat ion. Demulsification tests were performed at room temperature (25 °C). Demulsification results obtained via the bottle tests showed that the reference sample (blank) without CFA remained stable without water separation after 48 hrs while the addition of various CFA quantities (1 % to 7 %) brought about separation of water from the oil phase. Separation of water was observed to have increased with increasing CFA addition in the emulsion. Water separation continued for each sample until around 24 hrs when equilibr ium was attained, and water separation remained constant. The W/O emulsion containing 7 % CFA displayed the highest performance with demulsifica tion efficiency (DE) of 96.67%. Demulsification comparison test results between CFA and a commercial demulsifier (poloxamer - 407) using same concentration and under room temperature showed that CFA was capable of separating water better than this commercia l demulsifier. This observation indicates that CFA can compete favorably with many commercia l demulsifiers available in the market. Additionally, the outcome of demulsification efficiency of 7% CFA at elevated temperatures (i.e., 60 °C and 80 °C) was around 98%. More importantly, the separated water at these elevated temperatures was clearer and contained lesser oil floccules than the separated water phase observed during demulsification tests conducted at room temperature (25 °C) condition. Shear rheology measurement reveals that CFA addition altered the viscoelastic characteristics at the crude oil/water interface at an aging time of 10 hrs and 55 mins. Viscous modulus remained stagnant while elastic modulus dropped significantly. Optical morphology revealed the phase transformation in the as-prepared W/O emulsion before and after the addition of CFA particles. The possible mechanism governing the demulsification of W/O emulsion driven by CFA particles was proposed. It is believed that this work will be relevant to petroleum exploration and refining operations.