Squamous cell carcinoma antigen (SCCA) is one of the most commonly detected cancer biomarkers for a variety of cancers. In this paper, a microfiber ring laser biosensor with a graphene oxide linking layer for SCCA detection was proposed and experimentally demonstrated. SCCA antibody immobilized on graphene oxide surface binds specifically to SCCA, and induces refractive index variation over the surface of the microfiber biosensor, which leads to a wavelength shift of the microfiber ring laser biosensor. The experimental results show that the proposed laser biosensor can detect SCCA with concentrations from 0.01 to 50 ng/mL, and the calculated detection limit can be as low as 1.3 pg/mL. Additionally, the label-free quantitative detection of SCCA using the proposed microfiber biosensor was verified experimentally according to the corresponding regression equation, and the results agree well with clinical examination detection. This constructed microfiber biosensor may have promising practical applications in analytical detection, medical diagnostics, etc.