Recent spectroscopic results in the emerging area of transition-metal NIR-to-visible upconversion are related. The examples of Ti(2+)-, Re(4+)-, and Os(4+)-doped materials showing upconversion illustrate GSA/ESA, GSA/ETU, and photon avalanche multiphoton excitation mechanisms, respectively. Strategies for manipulation of such upconversion processes using the spectroscopic or magnetic properties of the host material are described. High-resolution low-temperature continuous-wave absorption and emission and time-resolved emission experiments combine to yield information about energy splittings, intensities, and excited-state dynamics, and assist in the design and development of luminescent materials showing novel multiphoton excitation properties.