AbstractThis study attempts to develop a reproducible thin‐film formation technique called vacuum‐free (VF) lamination, which transfers thin films using elastomeric polymer‐based laminating mediators. Precisely, by controlling the interface characteristics of the mediator based on the work of adhesion, VF lamination is successfully performed for various thicknesses (from 20 to 240 nm) of a conjugated photoactive material composed of poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl‐3‐fluoro)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐bʹ]dithiophene))‐alt‐(5,5‐(1ʹ,3ʹ‐di‐2‐thienyl‐5ʹ,7ʹ‐bis(2‐ethylhexyl)benzo[1ʹ,2ʹ‐c:4ʹ,5ʹ‐cʹ]dithiophene‐4,8‐dione)] (a polymer donor) and 2,2ʹ‐((2Z,2ʹZ)‐((12,13‐bis(2‐butyloctyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2ʹʹ,3ʹʹ:4ʹ,5ʹ]thieno[2ʹ,3ʹ:4,5]pyrrolo[3,2‐g]thieno[2ʹ,3ʹ:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (a nonfullerene acceptor). Interestingly, the organic photovoltaic and photodetecting applications, prepared by the VF lamination process, showed superior performance compared to those of devices prepared by conventional spin‐coating. This is due to the overturned surface morphology, which led to enhanced charge transport ability and blocking of the externally injected charge. Thus, the reproducible VF lamination process, exploiting an adhesion‐based elastomeric polymer mediator, is a promising thin‐film formation technique for developing efficient next‐generation organic optoelectronic materials consistent with the solution process.