In this study, a promising film formation technique is highlighted, named mold-assisted decal-coating, as a thin film transfer printing process using the polyurethane acrylate-based stamping mold. By optimizing the surface energy of the mold with wetting coefficient theory, the mold-assisted decal-coating process is successfully demonstrated by transferring the photoactive layer composed of the polymer donor, poly[4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)] and a narrow bandgap non-fullerene acceptor (NFA), 2,2′-[[4,4,9,9-tetrakis(4-hexylphenyl)-4,9-dihydros-indaceno[1,2-b:5,6-b′]dithiophene-2,7-diyl]bis[[4-[(2-ethylhexyl)oxy]-5,2thiophenediyl]methylidyne(5,6-difluoro-3-oxo-1H-indene-2,1(3H)-diylidene)]] bis[propanedinitrile]. This process induces a well-ordered morphology of photoactive material, prevents damage to the underlying layer by suppressing the solvent penetration. Both photovoltaic cells and photodetectors prepared by the decal-coated photoactive layers containing fluorinated NFAs showed higher performance (power conversion efficiency = 10.69% and specific detectivity = 1.27 × 10 12 A cm Hz 1/2 W −1 , respectively) than those of cells prepared by the spin-coating method owing to morphology inversion and smoother interface that led to suppressed internal resistance and enhanced charge flow in normal structure. Thus, the reproducible decal-coating process using a customized elastomeric mediator is an important thin film coating technique for efficient next-generation organic optoelectronic materials.