The tavorite polymorph of LiFeSO4F has attracted considerable attention as a cathode material for lithium ion batteries due to interesting structural and electrochemical characteristics. For the analysis of such iron-based electrode materials, Mössbauer spectroscopy has become an important and highly useful tool. In this work, we perform a detailed Mössbauer study of pristine tavorite LiFeSO4F prepared by an optimized synthesis in tetraethylene glycol as reaction media. In contrast to many reported results, we demonstrate the use of an asymmetric fitting model for the inner doublet of the spectrum, which is coupled to the structural properties of the compound. Moreover, we discuss a new approach of ascribing the Fe2 + -doublets to the two distinct crystallographic iron sites of tavorite LiFeSO4F by comparing the Mössbauer signal intensities with the expected f-factors for the corresponding iron atom.