Transition metal nitride materials exhibit unique optical characteristics and have attracted much interest for various applications, including waveguiding, photovoltaics, and nonlinear optical devices. Herein, titanium nitride (TiN), as a typical representative of biocompatible transition metal nitrides, is prepared and modified with gold nanoclusters (Au NCs) for promoting the carrier mobility, and the corresponding physical characteristics are systematically characterized. The TiN‐based saturable absorber (SA) on microfiber is fabricated and its nonlinear optical absorption property is also studied experimentally. Furthermore, the TiN‐decorated SA is applied in an ultrafast fiber laser at the communication bands. The fiber laser can generate the stable ultrashort pulses with a pulse width of 1.66 ps, a fundamental repetition rate of 7.49 MHz, and a spectral bandwidth of 2.61 nm. More importantly, the chaotic multiple pulses can be obtained, which is reported for the first time in the fiber laser based on the TiN SA on microfiber as far as it is known. The chaotic multiple pulses show many interesting characteristics, including high average pulse energy, varying pulse separations, and pulse intensities. These results have proved that the TiN shows great potential in many fields, such as advanced optical‐intensity modulator, ultrafast pulse dynamics, and optical fiber communications.