Graphene oxide carboxylic acid (COOH), a novel two-dimensional (2D) layered material with its unique optical and electronic properties, is discovered to exhibit the saturation of optical absorption under laser illumination. Applying the liquid-phase exfoliation method, we prepare graphene oxide-COOH dispersions with deionized water and fabricate graphene oxide-COOH polyvinyl alcohol polymer composite film. We further obtain stable Q-switching pulse and mode-locked laser operation with a 22.7 MHz repetition rate and a 1.5 ps pulse duration by incorporating the graphene oxide-COOH-based saturable absorbers into the all-fiber erbium-doped fiber laser cavity. The experimental results show that the proposed graphene oxide-COOH material can act as an effective absorber for pulsed fiber lasers, which demonstrate potential applications in the area of ultrafast optics.