In this paper, we described a method of double-sided diffusion and drift of lithium-ions into monocrystalline silicon for the formation of the large-sized, p-i-n structured Si(Li) radiation detectors. The p-i-n structure is a p-n junction with a doped region, where the “i-region” is between the n and the p layers. A well-defined i-region is usually associated with p or n layers with high resistivities. The p-i-n structure is mostly used in diodes and in some types of semiconductor radiation detectors. The uniqueness of this method is that, in this method, the processes of diffusion and drift of lithium-ions, which are the main processes in the formation of Si(Li) p-i-n structures, are produced from both flat sides of cylindrical-shaped monocrystalline silicon, at optimal temperature (T = 420 °C) conditions of diffusion, and subsequently, with synchronous supply of temperature (from 55 to 100 °C) and reverse bias voltage (from 70 to 300 V) during drift of lithium-ions into silicon. Thus, shortening the manufacturing time of the detector and providing a more uniform distribution of lithium-ions in the crystal volume. Since, at present, the development of manufacturing of large-sized Si(Li) detectors is hindered due to difficulties in obtaining a uniformly compensated large area and time-consuming manufacturing process, the proposed method may open up new possibilities in detector manufacturing.