The evaluation of wine adulteration is often a cumbersome process not exempt from multiple difficulties. In this work, a valuable methodology to rapidly assess wine adulteration was used. Harnessing the ratio of Compton and Rayleigh scattering signals obtained in TXRF (total reflection X-ray fluorescence). The Compton/Rayleigh signal ratio as a sensitive way to estimate the average effective atomic number (Zeff) of a sample was used. Thus, any addition made into the wine, would cause a change in its Zeff which could be detected by TXRF. Non-adulterated and adulterated wines were selected and its Zeff was estimated. The method was developed using X-ray excitation Molybdenum tube. Deconvolution of independent Compton and Rayleigh signals was performed by non-Gaussian and Gaussian curve resolution methods, and the area ratio was evaluated. A calibration curve for Compton/Rayleigh signal ratio versus Zeff was established and wine adulterated samples were tested in a Zeff range between 4.3 and 7.2. Wine adulteration was detected in all cases. The method is simple, fast, sensitive, precise and non-destructive. It procedure is usefulness as an important tool for wine industry and for the maintenance of origin and quality of wines.