Flexible, transparent, and moisture-impermeable materials are critical for packaging applications in electronic, food, and pharmaceutical industries. Here, we report that a single graphene layer embedded in a flexible polymer reduces its water vapor transmission rate (WVTR) by up to a million-fold. Large-area, transparent, graphene-embedded polymers (GEPs) with a WVTR as low as 10-6 g m-2 day-1 are demonstrated. Monolayered graphene, synthesized by chemical vapor deposition, has been transferred onto the polymer substrate directly by a very simple and scalable melt casting process to fabricate the GEPs. The performances of the encapsulated organic photovoltaic (OPV) devices do not vary even after subjecting the GEPs to cyclic bending for 1000 cycles. Accelerated aging studies of working OPV devices encapsulated in the GEPs show a 50% lifetime of equivalent to 1 000 000 min, which satisfies the requirements of organic electronics. © 2016 American Chemical Society.