Molecular interactions at interfaces have a significant effect on the wetting properties of surfaces on a macroscale. Sum frequency generation (SFG) spectroscopy, one of a few techniques capable of probing such interactions, generates a surface vibrational spectrum sensitive to molecular structures and has been used to determine the orientation of molecules at interfaces. The purpose of this review is to assess SFG spectroscopy's ability to determine the molecular orientations of interfaces composed of fluorinated organic molecules. We will explore three different types of fluorinated organic material-based interfaces, naming liquid-air, solid-air, and solid-liquid interfaces, to see how SFG spectroscopy can be used to gain valuable and unique information regarding the molecular orientation of each interface. We hope this review will help to broaden the understanding of how to employ SFG spectroscopy to obtain more complex structural information for various fluorinated organic material-based interfaces in the future.