Square-net materials are well positioned to lead optical spectroscopic explorations into the electronic structure, photoinduced dynamics, and phase transitions in topological semimetals. Hundreds of square-net topological semimetals can be prepared that have remarkably different electronic and optical properties despite having similar structures. Here we present what has been gleaned recently from these materials with the whole gamut of optical spectroscopies, ranging from steady-state reflectance and Raman investigations into topological band structures, electronic correlations, and equilibrium phase transitions to time-resolved techniques used to decipher ultrafast relaxation dynamics and nonequilibrium photoinduced phase transitions. We end with a discussion of some major remaining questions and possible future research directions.