Azoisobutylnitrile (AIBN) initiator was used in the treatment of most widely used domestic plastics in lieu of catalysts. The pyrolysis of low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP), poly-ethylene terephthalate (PET) and polystyrene (PS) plastics with azoisobutylnitrile was carried out individually under nitrogen atmosphere. A series of single (plastic/AIBN) and binary (mixed plastics/AIBN) reactions were carried out in a 25-cm(3) micro-autoclave reactor. The optimum conditions selected for this study were: 5% AIBN by weight of total plastics, 60 min, 650 psi and 420 degrees C. It was found that HDPE, LDPE, PP underwent to a maximum cracking and produced highest amounts of liquid and gaseous products. Pyrolysis of PET and PS plastics with AIBN afforded comparatively significant amount of insoluble organic materials. In other reactions, fixed ratios of mixed plastics were pyrolyzed with AIBN that afforded excellent yields of liquid hydrocarbons. This result shows a very significant increase in the liquid portions of the products on using AIBN in the pyrolysis of plastics. The use of AIBN in the pyrolysis of plastics is seems to be feasible and an environmental friendly alternative to catalytic process for maximizing the liquid fuels or chemical feed stocks in higher amounts.