Inkjet-printed electronics using metal particles typically lack electrical conductivity and interfacial adhesion with an underlying substrate. To address the inherent issues of printed materials, this Research Article introduces advanced materials and processing methodologies. Enhanced adhesion of the inkjet-printed copper (Cu) on a flexible polyimide film is achieved by using a new surface modification technique, a nanostructured self-assembled monolayer (SAM) of (3-mercaptopropyl)trimethoxysilane. A standardized adhesion test reveals the superior adhesion strength (1192.27 N/m) of printed Cu on the polymer film, while maintaining extreme mechanical flexibility proven by 100 000 bending cycles. In addition to the increased adhesion, the nanostructured SAM treatment on printed Cu prevents formation of native oxide layers. The combination of the newly synthesized Cu ink and associated sintering technique with an intense pulsed ultraviolet and visible light absorption enables ultrahigh conductivity of printed Cu (2.3 X 10(-6) Omega.cm), which is the highest electrical conductivity reported to date. The comprehensive materials engineering technologies offer highly reliable printing of Cu patterns for immediate use in wearable flexible hybrid electronics. In vivo demonstration of printed, skin-conformal Cu electrodes indicates a very low skin-electrode impedance (<50 k Omega) without a conductive gel and successfully measures three types of biopotentials, including electrocardiograms, electromyograms, and electrooculograms.