The increasing importance of goat milk renews the need to examine the authenticity of goat milk powder and to identify frauds with cow milk powder. The use of front-face and time-resolved fluorescence techniques to identify biochemical composition and structure changes could assist milk powder frauds analysis. This study aimed to use fluorescence spectra and lifetimes to differentiate frauds of goat milk powder with cow milk powder. We analyzed the fluorescence spectra by partial least squares and found a good prediction result. Employing analysis of variance, we observed different fluorescence lifetimes for goat milk powder with cow’s milk powder in six categories. In addition, we use linear regression to create a model to predict the amount of cow’s milk in each the samples using the mean intensity lifetime. These results indicate that front face and time-resolved fluorescence can assist on the analysis of powder milk and its composition.