Raman spectroscopy facilitates accurate and minimally invasive investigation on biomedical samples to reveal their molecular-level biological information. In this work, the cancer field effects of squamous cell carcinoma (SCC) tissues were illustrated by Raman microspectroscopy. Referenced with hematoxylin and eosin (H&E) stained microscopic images, the biochemical variations during SCC progress were meticulously described by the Raman spectral features in different pathological areas of two lesion types, including the biochemical changes in collagen, lipids, DNA, and other components of SCC diffusion and metastasis. The experimental results demonstrated that the intensities of the Raman peaks representing collagen (853, 936, and 1248 cm-1) were decreased, whereas the intensities of peaks corresponding to DNA (720, 1327 cm-1) and lipids (1305 cm-1) were increased significantly in cancerous lesions, which testified that SCC originates from the epidermis and invades the dermis gradually. The achieved results not only described the molecular mechanism of skin carcinogenesis, but also provided vital reference data for in vivo skin cancer diagnosis using Raman spectroscopy.