Simultaneous measurements of γ-ray and conversion electron Mössbauer spectra of Fe thin films under total reflection (TR) conditions were performed using an 57Fe synchrotron Mössbauer source. The correlation between the spectral shape for the TR of γ-rays and that of conversion electrons emitted from the Fe film is demonstrated. Two specific phenomena were observed for the first time, (i) suppression of the conversion channel under TR conditions and (ii) pure nuclear TR from one atomic layer of 57Fe embedded in the thin film. In particular, the latter enables a surface Mössbauer analysis at a resolution of monolayer with a measurement time in the order of a minute. This paves the way for further applications in studies on functional magnetic thin films.