Optical methods to detect breast cancer on the basis of its increased opacity have been explored for some time. These methods have matured to a point in which they are capable of quantifying the optical properties of breast tissue and translating them into measures of concentrations of relevant tissue components. In particular, near-infrared spectroscopy has been employed to determine the concentrations of hemoglobin, water, and lipids, as well as oxygen saturation of hemoglobin and optical scattering properties in normal and cancerous breast tissue. Dynamic optical measurements can also identify abnormal hemodynamic patterns associated with breast cancer. We review, in this article, a number of results in the field, which show that cancerous tissue is associated with higher hemoglobin and water concentrations, and a lower lipid concentration with respect to normal breast tissue. Indications that breast cancers are characterized by lower hemoglobin saturation and stronger scattering decay as a function of wavelength are less robust, with variable results reported in the literature. Intrinsic sources of optical contrast associated with breast cancer can also be used to monitor individual response to neoadjuvant therapy.