Time of flight secondary ion mass spectrometry (TOF-SIMS) was used to analyse the surface of two different types of pyrochlore, high Fe pyrochlore and low Fe pyrochlore, from Niobec Saint-Honore mine deposit. Pyrochlore grains were analysed in order to identify a potential relationship between pyrochlore matrix composition, the corresponding surface expression and the related effect on cationic collector adsorption. TOF-SIMS analyses of pyrochlore surfaces from a conditioning test show that the species indicative of the cationic collector, favour the surface of Fe poor pyrochlore relative to the Fe rich variety. Lower collector signals on the surface of the Fe-pyrochlore are matched by higher relative intensities of Fe, OH, O and FeOH. The TOF-SIMS results illustrate a negative relationship between a cationic collector adsorption and the presence of Fe and Fe oxidation species on the surface of pyrochlore grains, and supports previous work which identified a negative correlation between matrix Fe content and pyrochlore floatability. The surface analysis illustrates the link between pyrochlore matrix chemistry, the expression of surface species and their effect on collector adsorption.