The results of synthesis of alkyl-tert-alkyl ethers and esters in the presence of sulfonated graft copolymers of styrene with polyethylene, polystyrene, atactic polypropylene, ethylene-propylene rubber, etc. are reported. The possibility of getting methyl-tert-butyl, ethyl-tert-butyl, and propyl-tert-butyl ethers, and components of synthetic oils in the presence of the above-noted catalysts is shown.Ethers and esters are used widely as synthetic lube oils, high-octane gasoline additives, plasticizers, solvents, etc. Addition of ethers and esters to fuels and oils improves some performance properties of these petroleum products and also reduces emission of noxious substances, including exhaust gases. In view of high demands for etherification (esterification) products, development of efficient catalytic systems for getting them is an urgent task [1, 2].The purpose of this work was to develop new sulfonic cation-exchanger type of polymeric catalysts for etherification reactions as well as to study the properties of the ethers (esters) obtained. F o r p r o d u c i n g e t h e r s , u s e w a s m a d e o f b i o e t h a n o l , m e t h a n o l , a n d i s o p r o p a n o l . T h e bioethanol was produced by the Ukrainian company Gallon, and it contained 99% of ethyl alcohol and its density was 789.3 kg/m 3 .Butylene-isobutylene fraction (BIF) produced at the Sumgait plant Sintez-kauchuk (Synthetic Rubber) was used as the olefinic feedstock. The composition of the BIF was (wt. %): propane 0.85, ethylene 0.17, isobutane 4.14, isobutylene 42.29, butene-1 28.49, butadiene-1.3-1.5, n-butane 4.67, and trans-butene-2 9.43. The BIF was dried over calcined aluminum oxide and stored in a leak-tight cylinder.Reaction of isobutylene contained in the BIF with alcohols was effected in a stainless steel reaction vessel provided with a manometer, a batching valve, and a thermocouple.