This article reviews the basic principles of frequency-domain near-infrared spectroscopy (FD-NIRS), which relies on intensity-modulated light sources and phase-sensitive optical detection, and its non-invasive applications to the brain. The simpler instrumentation and more straightforward data analysis of continuous-wave NIRS (CW-NIRS) accounts for the fact that almost all the current commercial instruments for cerebral NIRS have embraced the CW technique. However, FD-NIRS provides data with richer information content, which complements or exceeds the capabilities of CW-NIRS. One example is the ability of FD-NIRS to measure the absolute optical properties (absorption and reduced scattering coefficients) of tissue, and thus the absolute concentrations of oxyhemoglobin and deoxyhemoglobin in brain tissue. This article reviews the measured values of such optical properties and hemoglobin concentrations reported in the literature for animal models and for the human brain in newborns, infants, children, and adults. We also review the application of FD-NIRS to functional brain studies that focused on slower hemodynamic responses to brain activity (time scale of seconds) and faster optical signals that have been linked to neuronal activation (time scale of 100 ms). Another example of the power of FD-NIRS data is related to the different regions of sensitivity featured by intensity and phase data. We report recent developments that take advantage of this feature to maximize the sensitivity of non-invasive optical signals to brain tissue relative to more superficial extracerebral tissue (scalp, skull, etc.). We contend that this latter capability is a highly appealing quality of FD-NIRS, which complements absolute optical measurements and may result in significant advances in the field of non-invasive optical sensing of the brain.