This paper explores a new method for screening metabolites in an array format based on relative polarity using selective solvent dissolution. A synthetic cocktail of metabolites was spotted onto a hydrophobic silicon surface, and solubilised with solvents of varying polarity. The metabolites retained on the silicon surface after the solvent treatments were detected using time-of-flight static secondary ion mass spectrometry (ToF-sSIMS). Solvent-specific metabolite retention was clearly evident on multivariate analysis of the dataset, using principal component analysis. Selective removal of metabolites was observed when solvents with different polarity were used, with the metabolite retention or removal in most cases correlating to the polarity of the solvent used, although consideration of other forces in operation may be needed to arrive at fully predictable behaviours. This approach provides the basis for development of a technique to separate complex metabolites into simpler constituents in a metabolite array prior to identification and quantification using mass spectrometry. It is an analytical approach that is intermediate between the more rapid but less informative direct analysis methods (such as DIMS) that do not involve any analyte separations and the more comprehensive but time consuming methods (such as GC- and LC-MS) that involve chromatographic or electrophoretic separations. The approach has the potential to be successfully developed for rapid, yet informative screening of metabolomes.