The shrink induced graphene composites based on layer-by-layer (LbL) self-assembly technique reported in this paper demonstrates controllably tunable features different from the conventional graphene composites. By self-assembly of graphene nanoplatelets on a polyolefin (PO) shrink film substrate, the surface morphologies of the graphene composites were capable of turning through controlling the shrink temperature. SEM and AFM were used to analyze the graphene composites, demonstrating that the density of the graphene nanowrinkles was growing with the rising of shrink temperature. The sensitivity of a chemical sensor based on the graphene composites was investigated, and the surface wetting ability of the graphene composites was also studied. The tunable properties with shrink temperatures promise the graphene composites for potential applications to chemical sensing and microfluidics.