Review of the authors' works on the synthesis of polyimides (PIs) by the method of one-stage high-temperature polycondensation in an unusual solvent-molten benzoic acid (BA). Compared with a known synthesis in inert high-boiling solvents, synthesis in BA takes place under mild conditions (140°C, 1-2 hour) to give completely imidized PIs. The approach has a number of advantages. Due to catalysis of the first reversible stage of amiс acid (AA) formation and low equilibrium constant (K = 10-20 l/mol), the first stage disappears kinetically, and the imidization reaction becomes limiting. The process becomes less sensitive to the basicity of diamines; therefore, low reactivity diamines can be involved. Water is easily removed from the melt by evaporation, which makes the whole process irreversible. Specific features of the method are successfully used to control the microstructure of the chain copolyimides (statistical to multiblock) and to synthesize hyperbranched PIs and star-shaped PIs with narrow molecular weight distribution.