Due to their extremely large electron, hole, and exciton Bohr radii, lead salt (PbS, PbSe and PbTe) quantum dots (QDs) can achieve levels of quantum confinement that are not accessible to more commonly studied III-V and II-VI QDs. Thus, extreme quantum confinement can be attained for relatively large particles, which may mitigate deleterious surface effects and produce novel optical and electronic properties. Absorption and emission spectra of lead salt QDs indicate a series of well-defined transitions, which can be tuned across the entire near infrared region with high luminescence quantum yields. Despite the large energy spacing between transitions in PbSe QDs absorption spectra, theory continues to fail to explain the presence of a dipole-allowed transition at the second excitonic absorption feature. We probe the band-edge structure using two-photon excitation, which formally allows mixed-parity transitions and thus, provides complimentary information to traditional one-photon measurements. In PbSe QDs with one-photon absorption peaks between 1200–1450 nm, the first two-photon allowed optical transition occurs at the energy of the second, one-photon absorption peak. Thus, the two-photon excitation data provides direct evidence that the second absorption peak originates from a mixed parity transition and we assign this peak as a “1S–1P” transition.