People all over the world consume caffeinated beverages and hormones. However, in many countries, the inefficiency of wastewater treatment and the discharge of untreated sewage in rivers reshwater sources. The objective of this work is to detect the anthropogenic marker caffeine and its human metabolites, and its degradation products, as well tibolone in water samples from the Meia Ponte River, whichis one of the raw water providers for cities in the metropolitan region of Goiânia, Brazil. The samples were collected during two different hydrological periods, located at various points around the city of Goiânia. First, the samples were pre-concentrated and the analysis were performed in a high-resolution mass spectrometer. The analysis results showed that caffeine and its degradation products and tibolone were detected at all sampling points in the two hydrological periods. It indicates that in some collecting points, MPR receives a raw sewage discharge and that the sewage treatment plant could not remove/degrade the caffeine. In addition, the results indicate that no human caffeine metabolites were detected.