We study the acceleration of heavy nuclei at supernova remnant (SNR) shocks, taking into account the process of ionization. In the interstellar medium, atoms heavier than hydrogen, which start the diffusive shock acceleration (DSA), are never fully ionized at the moment of injection. We will show that electrons in the atomic shells are stripped during the acceleration process, when the atoms already move relativistically. For typical environment around SNRs, the dominant ionization process is the photoionization due to the background galactic radiation. The ionization has two interesting consequences. First, because the total photoionization time is comparable to the beginning of the Sedov–Taylor phase, the maximum energy which ions can achieve is smaller than the standard result of the DSA, which predicts Emax∝ZN. As a consequence, the structure of the cosmic-ray spectrum in the knee region can be affected. The second consequence is that electrons are stripped from atoms when they already move relativistically; hence, they can start the DSA without any pre-acceleration mechanism. We use the linear quasi-stationary approach to compute the spectrum of ions and electrons accelerated after being stripped. We show that the number of these secondary electrons is enough to account for the synchrotron radiation observed from young SNRs, if the amplification of the magnetic field occurs.