Although polydimethylsiloxane (PDMS) transfer during microcontact printing (mu CP) has been observed in previous reports, which generally focused on only one or a few different substrates, in this work we investigate the extent of PDMS transfer onto a series of surfaces with a wide range of hydrophobicities using an uninked, unpatterned PDMS stamp. These surfaces include clean silicon, clean titanium, clean gold, "dirty" silicon, polystyrene, Teflon, surfaces modified with PEG, amino, dodecyl, and hexadecyl monolayers, and also two loose molecular materials. The PDMS transferred onto planar surfaces is, in general, easily detected by wetting and spectroscopic ellipsometry. More importantly, it is detected by time-of-flight secondary ion mass spectrometry (ToF-SIMS) because of the sensitivity of this technique to PDMS. The effect of surface free energy on PDMS transfer in microcontact printing is investigated, and the relationship between the amount of PDMS in ToF-SIMS spectra and the surface tensions of initial surfaces is revealed. We show that PDMS transfer can be applied as a probe of surface free energies using ToF-SIMS, where PDMS preferentially transfers onto more hydrophilic surface features during stamping, with little being transferred onto very hydrophobic surface features. Multivariate curve resolution (MCR) analysis of the ToF-SIMS image data further confirms and clarifies these results. Our data lend themselves to the hypothesis that it is the free energy of the surface that plays a major role in determining the degree of PDMS transfer during mu CP.