In recent years, liquid biopsies, especially for detecting circulating tumor cells (CTCs), have received great attention for cancer diagnosis and treatment monitoring. For clinical diagnosis of prostate cancer (PCa), prostate specific antigen (PSA) has been widely used as a standard method for PCa screening. However, PSA diagnostic efficacy within early-stage PCa patients with a PSA level of 4–10 ng mL⁻¹ is always controversial. Therefore, the development of new methods to assist clinical PSA diagnosis is greatly desired. Herein, we report the fabrication of antibody-modified reduced graphene oxide films, which can be used to efficiently detect CTCs in PCa patients with PSA levels of 4–10 ng mL⁻¹. The antibody-modified reduced graphene oxide (rGO) films were fabricated by spray coating reduced graphene oxide solution onto a smooth glass slide and then modifying it with anti-epithelial cell adhesion molecules (anti-EpCAMs) and anti-prostate specific membrane antigen (anti-PSMA). The rGO films exhibited an excellent ability to capture CTCs from the blood of PCa patients with PSA levels of 4–10 ng mL⁻¹ and the efficiency could reach 60% (6/10). Our approach for highly efficient detection of CTCs in early-stage PCa patients may provide great potential in assisting clinical cancer diagnosis.