The relative adsorption of fluoroxanthates on several different coal pyrites has been found to depend on the degree to which the pyrite surfaces are oxidized. Maximum xanthate adsorption occurs in the absence of pyrite surface oxidation and is affected by the presence of polysulfides and metal‐deficient sulfides on the pyrite surface. The structure and electronic properties of the xanthate molecule may also affect its adsorption. 3‐(Trifluoromethyl)benzyl xanthate was found to selectively adsorb on pyrite vs. coal surfaces. Secondary ion mass spectrometry is a viable alternative to x‐ray photoelectron spectroscopy for detecting xanthate adsorption. © 1997 by John Wiley & Sons, Ltd.