The review presents the materials of a systematic scientific and technical analysis of the results of studying the problem of processing technical vegetable (tv-) oils, in particular rapeseed or soybean oils, into alternative fuels of a new type — biofuels as a reflection of a complex of modern factors of resource and energy saving, effective methods and technologies, ecological production safety and rational use. The information system for analyzing the development of this problem covers certain stages, in particular: a) the period from its formation at the level of research tasks with the development of the first processing method — methanolysis-ethanolysis of tv-oils and the technology of the so-called traditional biofuel production; b) formation of an algorithm for searching for perfect and effective methods of processing tv-oils with the achievement of the current state of the problem; c) comparative technical and economic analysis of traditional and innovative methods. It is noted that in the procedures for the search and development of effective methods for the production of biofuels, it is necessary to rely on the mechanisms of three typical, reversible reactions of transesterification of triacyl-glycerol molecules of tv-oils as esters underlying them, namely: a) alcoholysis of tv-oils with methanol or ethanol — at the heart of the methanolysis-ethanolysis method; b) esterolysis of tv-oils by non-oily, low molecular weight esters, in particular ethyl acetate — the methods of esterolysis are based on; c) acetolysis of tv-oils with acetate acid — the basis of the complex method “acetolysis — acylation of alcohols”. Significant disadvantages and imperfections of traditional methanolysis, which reduce its efficiency and quality of biofuel, are characterized. Their causes and consequences are reasonably considered. It was informed about the method we developed for the first time for the esterolysis of tv-oils with ethyl acetate and the technological foundations of biofuel production by it as a more perfect and efficient alternative to traditional methanolysis. Moreover, some of its shortcomings and their impact on fuel quality are noted. An innovative two-stage method of processing them according to the principle of “glycerolysis-2 — alcoholysis or esterolysis of mono-acyl-glycerols”, alternative to the one-stage methods of alcoholysis and esterolysis of tv-oils has been proposed. Its significant advantages in terms of efficiency and quality of biofuel have been proven. Another innovative two-stage method of processing tv-oils according to the principle of “acetolysis of tv-oils with obtaining a mixture of acid chlorides of high-liquid acids — acylation of ethanol or methanol with acid chlorides” with obtaining high-quality biofuel is described. It is shown that acetolysis of tv-oils should be considered as the basis of a complex method of production from them of any bioproduct of the tv-materials industry. Comparison of indicators of a number of properties of new biofuels obtained by different methods with mineral diesel fuel and composite min-bio-fuel showed the high quality of both biofuel itself and compositions with its addition. Bibl. 24, Fig. 1, Tabl. 4.