Due to the low vapor pressure of aniline, it is challenging to develop a specific rapid fluorescence detection material for low concentrations of aniline gas, which is suspected to result in carcinogenicity when people are exposed by ingestion, inhalation, and skin contact. Herein, the easy-preparing Schiff base ligands were employed to construct the binuclear cadmium(II) compounds featuring a good plane and fine luminescent property, and then, the end groups were changed, making the compounds metalloligands to further build the 3D metal-organic frameworks (MOFs), named MECS-2. It is found that MECS-2 can achieve specific luminescent enhancement response for aniline gas. Furthermore, a large-scale MECS-2a film could be easily prepared by electrospinning nanoMECS-2, which presents the highly efficient and visual detection for aniline gas with the luminescent enhancement effect up to 20 times and good repeatability. Our work provides a good example for the efficient construction of MOF-based films with the fluorescence detection function for organic aromatic gases.