The preparation process of 2, 3, 5, 6-tetrafluoro-para-xylyl alcohol with 2, 3, 5, 6-tetrachloro-p-phenyl diformyl chloride as material includes fluorination with potassium fluoride, etc. as fluorination agent, sulfolane, etc. as solvent and calixarene, etc. as catalyst and at 40-230 deg.c; esterification of ester with fatty alcohol or aromatic alcohol as esterifying agent and at 20-120 deg.c; reduction of ester with sodium borohydride, etc. as reductant and sulfolane, etc. as solvent, and at -10 deg.c to 60 deg.c; bromination with HBr acid as brominating agent and dichloromethane as solvent and at 30-160 deg.c; and reduction of bromide with magnesium powder, etc as reductant and fatty alcohol, water, chloride, etc as solvent, and at -10 deg.c to 50 deg.c. The present invention has the advantages of simple process, low production cost, high product yield and purity, and is suitable for industrial production.