Since the first discovery of Ti3C2 in 2011, two-dimensional (2D) transition-metal carbides, carbonitrides and nitrides, known as MXenes, have attracted significant attention. Due to their outstanding electronic, optical, mechanical, and thermal properties, versatile structures and surface chemistries, Ti3C2 MXenes have emerged as new candidates with great potential for applications in optoelectronic devices, such as photovoltaics, photodetectors and photoelectrochemical devices. The excellent metallic conductivity, high anisotropic carrier mobility, good structural and chemical stabilities, high optical transmittance, excellent mechanical strength, tunable work functions, and wide range of optical absorption properties of Ti3C2 MXene nanostructures are the key to their success in a number of electronic and photonic device applications. Herein, we summarize the fundamental properties and preparation of pure Ti3C2 MXenes, functionalized Ti3C2 MXenes and their hybrid nanocomposites, as well as their optoelectronic applications. In the end, the perspective and current challenges of Ti3C2 MXenes toward the development of advanced MXene-based nanostructures are briefly discussed for future optoelectronic applications.