Neutral poly(N-vinyl carbazole) (PVK) and perylene are coassembled within the interlayers of layered double hydroxide (LDH) nanosheets to form (perylene@PVK/LDH)(n) ultrathin films by the hydrogen-bond layer-by-layer assembly method. An efficient 2D fluorescence resonance energy transfer (FRET) process from PVK to perylene is demonstrated, and this FRET process can be inhibited/recovered reversibly by the adsorption/desorption of common volatile organic compounds (VOCs). [GRAPHICS] .