Electrospun nanofibrous hybrid materials have several advantageous characteristics, including easy preparation, high porosity, and a large specific surface area. Meanwhile, they can be more suitable for colorimetric detection in environmental and food areas than organic materials due to the advantages of inorganic nanomaterials, i.e., stability, low toxicity, and durability. In addition to being able to immobilize nanomaterials to avoid particle aggregation, electrospinning hybrid materials also have the advantages of high specific surface area and high porosity, which is beneficial for constructing colorimetric sensors. This review mainly summarizes the fabrication methods of electrospun nanofibrous hybrid materials and the application of electrospun nanofibrous hybrid material based colorimetric sensors. First, the preparation strategies of electrospun nanofibrous hybrid materials were discussed. Then, the applications of the obtained electrospun nanofibrous hybrid materials in the colorimetric sensors for environmental molecules in the gas and liquid phase were further investigated. Finally, this review looks forward to the development prospects and challenges of electrospun hybrid materials in practical applications of colorimetric sensors in order to support the application of colorimetric sensors in practical detection.