Sub-ångström working regime refers to a working state of free-electron lasers which allows the generation of hard X-rays at a photon wavelength of 1 ångström and below, that is, a photon energy of 12.5 keV and above. It is demonstrated that the accelerators of the European X-ray Free-Electron Laser can provide highly energetic electron beams of up to 17.5 GeV. Along with long variable-gap undulators, the facility offers superior conditions for exploring self-amplified spontaneous emission (SASE) in the sub-ångström regime. However, the overall FEL performance relies quantitatively on achievable electron beam qualities through a kilometers-long accelerator beamline. Low-emittance electron beam production and the associated start-to-end beam physics thus becomes a prerequisite to dig in the potentials of SASE performance towards higher photon energies. In this article, we present the obtained results on electron beam qualities produced with different accelerating gradients of 40 MV/m–56 MV/m at the cathode, as well as the final beam qualities in front of the undulators via start-to-end simulations considering realistic conditions. SASE studies in the sub-ångström regime, using optimized electron beams, are carried out at varied energy levels according to the present state of the facility, that is, a pulsed mode operating with a 10 Hz-repetition 0.65 ms-long bunch train energized to 14 GeV and 17.5 GeV. Millijoule-level SASE intensity is obtained at a photon energy of 25 keV at 14 GeV electron beam energy using a gain length of about 7 m. At 17.5 GeV, half-millijoule lasing is achieved at 40 keV. Lasing at up to 50 keV is demonstrated with pulse energies in the range of a few hundreds and tens of microjoules with existing undulators and currently achievable electron beam qualities.