The 6S1/2-5D5/2 electric quadrupole transition of cesium is studied experimentally via Doppler-free spectroscopy in a hot vapor. With a three-level coupled system, the hyperfine structure of this transition is resolved. The intensities of the lines in the spectrum are investigated and the optical pumping dynamics are analyzed. Furthermore, a laser is stabilized to the 6S1/2-5D5/2 transition. This makes the presented setup a useful tool for further investigations of electric quadrupole transitions. Based on our results, we plan future experiments with laser-cooled atoms close to surfaces, e.g., to enhance the quadrupole coupling.