We described the effect of the ultraviolet ozone (UVO) treatment of a polydimethylsiloxane (PDMS) stamp on the fidelity of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) patterns produced from a TIPS-PEN/polymer blend by selective contact evaporation (SCE). During the SCE process, the TIPS-PEN in contact with the nanoporous PDMS was absorbed into the PDMS stamp, leaving out the TIPS-PEN patterns, complementary to the PDMS patterns, in the noncontact regions. For the case of the untreated, hydrophobic PDMS surface, the TIPS-PEN patterns developed initially were shrunken and eventually disappeared after 24 h due to the steady absorption of the TIPS-PEN in time. In contrast, for the UVO-treated case, the TIPS-PEN patterns were found to maintain the initial shapes over the period of 24 h since the absorption of the TIPS-PEN was limited by the hydrophilic nature of the UVO-treated PDMS. The modified PDMS surface by the UVO for 30 min yielded the highest fidelity of the TIPS-PEN patterns in both height and width. The patterned TIPS-PEN layer by the SCE was implemented into an organic field-effect transistor to demonstrate the viability of the SCE combined with the UVO treatment for solution-processed organic electronic devices.