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The stamping process of self-assembled monolayers (SAMs) with polydimethylsiloxane (PDMS) mold on the Ag electrode was demonstrated, for use as the anode of a top-emission organic light-emitting device (OLED) and the cathode of an organic photovoltaic (OPV) device stacked underneath. Such SAMs reduce the barrier for hole injection from the Ag to the hole-transport layer of OLED. The PDMS mold coated with SAMs can be used repeatedly, for more than nine times. In this tandem device, the power conversation efficiency under OPV-mode operation and the current efficiency under OLED-mode operation were nearly identical to those in individual devices without compromise.