We report the observation of laser-assisted electron diffraction (LAED) through the collision of 1 keV electrons with gas-phase CCl4 molecules in a femtosecond near-infrared laser field. In the angular distribution of the scattered electrons with the energy shifts of ±ℏω, we observed clear diffraction patterns which reflect the geometrical structure of the molecules at the moment of laser irradiation. Our results demonstrate that ultrafast nuclear dynamics of molecules can be probed by LAED with the high temporal (<10 fs) and spatial (∼0.01 Å) resolutions.