Suitably designed electrochemiluminescence (ECL) carrying group acting as high-efficiency solid-state probe has attracted a lot of attention. Herein, molybdenum carbides with the two-dimensional ultrathin nanosheet structure on the surface and excellent conductivity were successfully employed as the nanocarriers for the capture of ECL reagent of luminol-capped Au nanoparticles (luminol-AuNPs). Notably, the luminol-AuNPs in the hybrid (luminol-AuNPs@Mo2C) exhibited enhanced ECL performance (∼6-fold) as compared to individual luminol-AuNPs because of the facilitated electron transfer process. Ultimately, the as-prepared ECL label was used to construct a label-free ECL immunosensor for the detection of α-fetoprotein (AFP). The immunosensor shows high selectivity and high sensitivity to AFP detection with a wide linear range of 0.1 pg·mL-1 to 30 ng·mL-1 and an extremely low detection limit of 0.03 pg·mL-1 (S/N = 3). Moreover, the fabricated ECL immunosensor exhibit satisfied performance in the practical application. This novel sensing strategy not only broadens the application of molybdenum carbides but also provides a new efficient approach to detect various biomolecules.