Flexible nanolithographic and printing methods are essential tools in the field of nanoscience and nanotechnology. [1][2][3][4][5] Scanning probe techniques such as dip-pen nanolithography (DPN) [3,[6][7][8][9][10][11][12] and nanografting [13,14] are extremely useful since they allow one to make nanostructures from a wide variety of different chemical compositions. In the case of DPN, despite significant advances in parallelization, [2,[15][16][17] it is still challenged for certain applications with regard to throughput, especially when compared to lower resolution contact printing methods. Indeed, microcontact printing (ÎŒCP) has emerged as a "bench-top" technique for preparing patterns of various active structures in a massively parallel manner. [18][19][20] In conventional ÎŒCP, a soft elastomer stamp (typically polydimethylsiloxane, PDMS) with relief structures predefined by photo-or e-beam lithography is brought into contact with a substrate, where the ink is transferred from the stamp to the substrate surface at the area of contact.[21] PDMS has a Young's Modulus of 1 MPa, which is soft enough to make conformal contact with planar or nonplanar surfaces to facilitate ink transfer. However, since the relief structures are separated by air voids in the stamp, the mechanical instability (pairing, sagging, etc.) of the stamp deriving from the "soft" nature of PDMS, has been a major limitation for a variety of applications in ÎŒCP.[5,22,23] The volatility of the inks and their diffusion properties on a surface also can be limiting factors when printing small features (Scheme 1).[24] Although many solutions have been suggested to address both mechanical and ink-transport issues, such as using harder elastomers [25,26] and establishing control over printing time, [27] the lateral resolution of printed features and the design of such stamps are still limited to ~150 nm (in terms of alkanethiols) and a ~1/20 filling factor, respectively. [23,28] Herein, we report how one can use DPN to prepare a stamp for high resolution ÎŒCP in a way that keeps the PDMS surface topographically flat but chemically patterned. The mechanically stable flat stamp is prepared without a photomask (since the structure may be directly written onto the surface by DPN), and the pattern drawn by DPN combined with subsequent chemical modification of the exposed areas of the stamp, allows one to create a surface with well-defined chemical regions that can be used to confine ink transport to sub-100 nm dimensions and prevent the lateral diffusion of the ink (Scheme 1). Others have used contact inking, [29,30] metal contact masks, [31,32] and template-mediated selfassembly approaches[33] to fabricate (sub)micron-sized chemical patterns on PDMS, but the approach described herein is remarkably simple and straightforward to implement and does not require complex and expensive photo-or e-beam lithography. More importantly, the high registration and resolution of DPN allow one to create stamps using this approach that ** C.A.M. acknowledges the AFOSR, DA...