Results of investigation of fractional distillation of straight-run gasoline-pyrolysis pyrocondensate to concentrate unsaturated hydrocarbons for synthesis of polymeric resins are reported. The fractional and hydrocarbon composition of the liquid-pyrolysis product is determined. The effect of polymerization inhibitors on the fractionation process is evaluated in view of the presence of thermally unstable hydrocarbons in the product. The vapor-liquid equilibrium in the binary mixtures formed by the pyrocondensate components is studied experimentally, and a mathematical model of the liquid-vapor phase space is built. A process-flow diaphragm is proposed for pyrocondensate fractionation, which allows for separation of the components into distillate for synthesizing light petropolymeric resins such as styrene, methyl styrenes, vinyl toluenes, etc. The parameters of the batch-operating distillation tower are determined.