The invention discloses a photoelectric composite medium-voltage trailing cable with rated voltage of 12 / 20kV-26 / 35kV for a mine and a preparation process of the cable. The medium-voltage trailing cable comprises a photoelectric unit, a ground wire core and at least three power line core conductors; and according to a formula, an inner sheath layer and an outer sheath layer comprise the following materials of 35-45 percent of chloroprene rubber 320F, 0.9-1.1 percent of tetramethyl thiuram disulfide, 0.45-0.55 percent of 2-thiobenthothiazole, 0.45-0.55 percent of 2-mercapto benzimidazole, 0.35-0.45 percent of N,N'-bi(beta-naphthyl) p-phenylenediamine, 0.5-0.7 percent of stearic acid, 4.5-5.5 percent of dioctyl sebacate, 0.9-1.1 percent of magnesium oxide, 0.9-1.1 percent of zinc oxide, 7-9 percent of a composite flame retardant, 4.5-5.5 percent of tricresyl phosphate, 17-23 percent of highly abrasion-resistant carbon black, 5.5-6.5 percent of talcum powder serving as a filling agent and 10-12 percent of calcium carbonate serving as a filling agent. According to the photoelectric composite medium-voltage trailing cable, the power transmission and signal transmission performances at the environmental temperature of 40 DEG C below zero to 80 DEG C are realized, and the ultraviolet resistance, low temperature resistance, wear resistance and ageing resistance are improved.