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Potential advances in sensing can be made by conjugated polymers includes poly(p-phenylene), poly(p-phenylene vinylene), polyfluorene, and poly(thiophene). Among the most important classes of polymers are heterocyclic polymers, such as polyimides, because polyimide nanocomposites possess exceptional mechanical strength as well as chemical, mechanical and temperature resistance. Polyimide offers the potential of providing efficient sensors through its ability to work actively. There is evidence that fluorescent polyimide is efficient at detecting hazardous pollutants. Chemical modifications of the polyimide backbone gave rise to an improved luminescence efficiency of polyimide by incorporating fluorescent chromophores. An overview of recent developments in fluorescent polyimide in sensing applications is presented in this chapter. Some of the fluorescent polyimide materials prepared from different types with surface modification (type-1: perylene tetracarboxylic dianhydride and oxydianiline) (type-2: Tetra (4-aminophenyl) porphyrin and perylenetracarboxylic dianhydride) and (type-3 2-(4,4′-diamino-4′′-triphenylamine)-5-(4-dimethylaminophenyl)-1,3,4-oxadiazole) etc. In the following section, the methods and sensing mechanism of fluorescent polyimide are described.