Chromium oxide (Cr2O3) is a promising material used in the applications such as photoelectrochemical devices, photocatalysis, magnetic random access memory, and gas sensors. But, its nonlinear optical characteristics and applications in ultrafast optics have not been studied yet. This study prepares a microfiber decorated with a Cr2O3 film via magnetron sputtering deposition and examines its nonlinear optical characteristics. The modulation depth and saturation intensity of this device are determined as 12.52% and 0.0176 MW/cm2. Meanwhile, the Cr2O3-microfiber is applied as a saturable absorber in an Er-doped fiber laser, and stable Q-switching and mode-locking laser pulses are successfully generated. In the Q-switched working state, the highest output power and shortest pulse width are measured as 12.8 mW and 1.385 µs, respectively. The pulse duration of this mode-locked fiber laser is as short as 334 fs, and its signal-to-noise ratio is 65 dB. As far as we know, this is the first illustration of using Cr2O3 in ultrafast photonics. The results confirm that Cr2O3 is a promising saturable absorber material and significantly extend the scope of saturable absorber materials for innovative fiber laser technologies.