In this study, the investigation on effect of plastic during co-pyrolysis with biomass has been carried out in a fixed reactor. Pyrolysis of neem wood bark (NB), low density polyethylene (LDPE) and their blends at different ratios is performed in order to evaluate the product distribution. The effects of reaction temperature, NB-to-LDPE blend ratio on product distribution and chemical compositions of bio-oil are examined. The co-pyrolysis of NB and LDPE increased the yield and quality of the bio-oil. The experiments are conducted under different LDPE addition percentage such as 20%, 40%, 50%, 60% and 80%. Under the optimum experimental condition of 60% addition of LDPE and temperature of 450°C, the maximum yield of bio-oil (64.8 wt%) and hydrocarbon (75.2%) are achieved with the lowest yield of oxygenated compounds. The calorific value of the co-pyrolytic oil is found to be higher than that of NB pyrolytic oil. The relation between NB and LDPE during co-pyrolysis has been validated by GC–MS analysis, which shows in decrease of oxygenated compounds.