The poor air and thermal stability of organic-inorganic halide perovskite solar cells have hindered their real applications. Here we report the insertion of a chemical vapor deposited graphene between the Au electrode and spiro-OMeTAD in planar perovskite solar cells to block the diffusion of air and Au into the perovskite layer, where the single layer graphene is transferred into the devices by a simple laminated process. After ageing in 45% humidity air for 96 h or thermal annealing at 80 °C for 12 h, more than 94% PCE of the devices with graphene can be maintained, which is much better than that of devices without graphene (∼57%). The improved stability of devices with the graphene layer is attributed to the reduction of carrier recombination from decomposition of the perovskite layer in air or Au doping into the perovskite layer under annealing treatment. Therefore, graphene is a promising ultra-thin barrier against air and metal diffusion, and has potential applications in photovoltaic devices, integrated circuit chips and light emitting diodes.