We have developed a compact relativistic femtosecond electron diffractometer with a radio-frequency photocathode electron gun and an electron lens system. The electron gun generated 2.5-MeV-energy electron pulses with a duration of 55 ± 5 fs containing 6.3 × 104 electrons per pulse. Using these pulses, we successfully detected high-contrast electron diffraction images of single crystalline, polycrystalline, and amorphous materials. An excellent spatial resolution of diffraction images was obtained as 0.027 ± 0.001 Å−1. In the time-resolved electron diffraction measurement, a laser-excited ultrafast electronically driven phase transition in single-crystalline silicon was observed with a temporal resolution of 100 fs. The results demonstrate the advantages of the compact relativistic femtosecond electron diffractometer, including access to high-order Bragg reflections, single shot imaging with the relativistic femtosecond electron pulse, and the feasibility of time-resolved electron diffraction to study ultrafast structural dynamics.