As a new class of 2D materials, MXenes have attracted a lot of interest because of their prominent performance in versatile applications, such as batteries, supercapacitors, catalysts, electronics, and optics. In this work, an all‐optical modulator using MXene Ti3C2Tx deposited on a microfiber is proposed. By inserting an MXene‐deposited phase shifter into one arm of a Mach–Zehnder interferometer, the MXene Ti3C2Tx absorbs the control light and generates heat, which induces significant refractive index changes through strong light–matter interactions and thermo‐optic effects. In this study, a maximum phase shift of 16π is obtained, and an efficient all‐optical switch with an extinction ratio of more than 18.53 dB and a rise time constant of 4.10 ms are demonstrated. The advantages of this modulator include its all‐fiber content, low cost, ease of integration, and compactness. All‐optical modulators based on thermo‐optical effects will play an active role in the future of optical communications and optical information processing.