The manufacturing of polystyrene around the globe has escalated in the past years due to its huge applications in various areas. The perpetual market needs of polystyrene led the polystyrene wastes accretion in the landfill causing environmental deterioration. The soaring need for polystyrene also led to the exhaustion of petroleum, a non-renewable energy source, as polystyrene is a petroleum-derived product. Researchers from around the world have discovered a few techniques to take care of the polystyrene scraps, namely recycling and energy recovery techniques. Nevertheless, there are demerits involved with recycling techniques, such as they call for huge labor expenses in the separation process and cause water pollution, thereby decreasing the process sustainability. Owing to these demerits, the researchers have focused their attention on the energy recovery technique. Since petroleum is the main ingredient of polystyrene synthesis, the restoration of liquid oil from polystyrene via the pyrolysis method is a promising technique as the recovered oil has greater calorific value as compared to commercially available fuel. The present paper surveys the pyrolysis technique for polystyrene and the important process parameters that control the end product, like oil, gas, and char. The chief process parameters that are discussed in this review paper include the type of reactors, temperature, residence time, pressure, catalyst types, type of fluidizing gases, and their flow rate. A more recent technique of utilizing a solvent to perform pyrolysis and the effect of various process conditions on the product yield have been discussed. Apart from this, various outlooks to optimize the liquid oil recovery from polystyrene are also reviewed.