One of the frontiers in electron scattering is to couple ultrafast temporal resolution with highly localized probes to investigate the role of microstructure on material properties. Here, taking advantage of the unprecedented average brightness of the APEX electron gun providing relativistic electron pulses at high repetition rates, we demonstrate for the first time the generation of ultrafast relativistic electron beams with picometer-scale emittance and their ability to probe nanoscale features on materials with complex microstructures. At the sample plane, the APEX beam is tightly focused by a custom in-vacuum lens system based on permanent magnet quadrupoles, and its evolution around the waist is tracked by a knife-edge technique, allowing accurate reconstruction of the beam shape and local density. We then use the focused beam to characterize a Ti-6 wt% Al polycrystalline sample by correlating the diffraction and imaging modality, showcasing the capability to locate grain boundaries and map adjacent crystallographic domains with sub-micron precision. This work provides a new paradigm for ultrafast electron instrumentation, demonstrating the ability to generate relativistic beams with ultrasmall transverse phase space volumes enabling novel characterization techniques such as relativistic ultrafast electron nano-diffraction and ultrafast scanning transmission electron microscopy.Since the discovery of the particle-wave duality 1 , electrons have been extensively used to probe matter at atomic scales. Owing to their very short (sub-Å) wavelength and large scattering cross section compared to X-rays, electron diffraction and imaging are today well established techniques for structure determination. More recently, the advent of ultrafast lasers sparked the development of intense ultrashort electron sources which, in turn, paved the way to a new generation of time-resolved electron scattering techniques such as ultrafast electron diffraction and microscopy (UED/M) 2-4 . These are now capable of probing atomic-scale structural dynamics with femtosecond-scale temporal accuracy.Recent developments in this field include the introduction of methods and technology common in particle accelerator science. Radio frequency (RF) based electron sources have been successfully used for generating few-femtosecond electron probe beams 5, 6 and for gathering information about ultrafast structural changes in solids and gases 7, 8 . Here, electrons are generated and rapidly accelerated to relativistic energies by using high accelerating gradients, increasing the maximum achievable electron current density 9, 10 and minimizing the temporal broadening caused by Coulomb repulsions and initial energy bandwidth, which are the main challenges for low-energy electron sources.Notwithstanding this significant progress, ultrafast electron-based instrumentation is still far from reaching spatial resolution similar to what can be achieved in static electron microscopes. At low energies, setups using tip-based photoemission guns in standard tra...