The experimental results prove the ability to realize technology of chemical heat treatment of some materials by surface alloying using a wide-aperture low-energy high-current electron beam. Doped hardened layers were produced due to initiating exothermic chemical reactions between the base and the thin film covered on it. Nevertheless, it is quite difficult to control the process of surface electron-beam alloying due to the significant variation in the parameters of the microsecond electron beam pulse and the instability of its interaction with the processed material. It leads to significant random changes that occur spontaneously, regardless of the control system. In this situation, it is proposed to use the method based on monitoring of oscillations and acoustic emission, which has long proved to be an effective tool in the study of phase transformations and plastic deformation. The appearance of a process with high vibroacoustic activity under irradiation of plates made of pre-nitrated steel 08Cr17Ti with a deposited film Nb70Hf22Ti8 in the range of 11–22 kHz 10 ms after the electronic pulse was experimentally shown on this background. The source of this vibroacoustic signal is a change in the microstructure of the alloy, including the appearance of a martensitic component in the near-surface layer of the sample caused by the formation of nitride based on niobium. Tracking changes in the effective value of the vibroacoustic signal allow choosing the rational modes of irradiation with electron-beam surface alloying, involving the supply of maximum power, limited by the possibility of evaporation of the film with alloying components.