Functional near-infrared spectroscopy (fNIRS) has been utilized already around three decades for monitoring the brain, in particular, oxygenation changes in the cerebral cortex. In addition, other optical techniques are currently developed for in vivo imaging and in the near future can be potentially used more in human brain research. This paper reviews the most common label-free optical technologies exploited in brain monitoring and their current and potential clinical applications. Label-free tissue monitoring techniques do not require the addition of dyes or molecular contrast agents. The following optical techniques are considered: fNIRS, diffuse correlations spectroscopy (DCS), photoacoustic imaging (PAI) and optical coherence tomography (OCT). Furthermore, wearable optical brain monitoring with the most common applications is discussed.