This paper puts forward a novel method of measuring the thin period-structure-film thickness based on the Bloch surface wave (BSW) enhanced Goos–Hänchen (GH) shift in one-dimensional photonic crystal (1DPC). The BSW phenomenon appearing in 1DPC enhances the GH shift generated in the attenuated total internal reflection structure. The GH shift is closely related to the thickness of the film which is composed of layer-structure of 1DPC. The GH shifts under multiple different incident light conditions will be obtained by varying the wavelength and angle of the measured light, and the thickness distribution of the entire structure of 1DPC is calculated by the particle swarm optimization (PSO) algorithm. The relationship between the structure of a 1DPC film composed of TiO2 and SiO2 layers and the GH shift, is investigated. Under the specific photonic crystal structure and incident conditions, a giant GH shift, 5.1 × 103 times the wavelength of incidence, can be obtained theoretically. Simulation and calculation results show that the thickness of termination layer and periodic structure bilayer of 1DPC film with 0.1-nm resolution can be obtained by measuring the GH shifts. The exact structure of a 1DPC film is innovatively measured by the BSW-enhanced GH shift.