Pyrolysis of low-density polyethylene (LDPE) was studied in order to relieve environmental pollution and recover the monomer or fuel. LDPE was thermally decomposed with and without catalyst. First, efficiency of oil production was analyzed according to the variation of reaction conditions such as reaction temperature, types of additives and catalyst, and contacting method. In non-catalytic LDPE pyrolysis, isothermal reaction was almost similar to non-isothermal reaction. Light oil was produced with low reaction temperature (430 °C) in the isothermal reaction, but low heating rate caused light oil production in the non-isothermal reaction. When pyrolyzed polyethylene (PE oil) was applied as an additive, no significant effect showed in the isothermal reaction. In catalytic LDPE pyrolysis (10%NiO/S-A) with additives, efficiency greatly increased especially with polystyrene (PS) addition. It was also found that the molecular weight distribution of product oil could be controlled by applying different additives. When a catalytic reactor was used, the amount of the low molecular weight compound increased as flow rate of thermally decomposed gas was lowered.