Photoelectric smoke detectors are the most cost-effective devices for very early warning fire alarms. However, due to the different light intensity response values of different kinds of fire smoke and interference from interferential aerosols, they have a high false-alarm rate, which limits their popularity in Chinese homes. To address these issues, an embedded spatial–temporal convolutional neural network (EST-CNN) model is proposed for real fire smoke identification and aerosol (fire smoke and interferential aerosols) classification. The EST-CNN consists of three modules, including information fusion, scattering feature extraction, and aerosol classification. Moreover, a two-dimensional spatial–temporal scattering (2D-TS) matrix is designed to fuse the scattered light intensities in different channels and adjacent time slices, which is the output of the information fusion module and the input for the scattering feature extraction module. The EST-CNN is trained and tested with experimental data measured on an established fire test platform using the developed dual-wavelength dual-angle photoelectric smoke detector. The optimal network parameters were selected through extensive experiments, resulting in an average classification accuracy of 98.96% for different aerosols, with only 67 kB network parameters. The experimental results demonstrate the feasibility of installing the designed EST-CNN model directly in existing commercial photoelectric smoke detectors to realize aerosol classification.