The synergetic effect between algae biomass in co-pyrolysis with synthetic plastics (polypropylene (PP), polyethylene (PE), and expanded polystyrene (EPS)) was investigated in this work. Individual feedstock pyrolysis and co-pyrolysis of algae with PP, PE, and EPS were conducted at a constant supply of microwave energy (420 J/s). Pyrolysis char was used as a susceptor in all the experiments. The average heating rate was varied in the range of ∼50–60 °C/min for achieving the final pyrolysis temperature of 600 °C. In catalytic co-pyrolysis, the ZSM-5 catalyst was used for upgrading the physicochemical properties of pyrolysis oil. The use of catalyst promoted the excessive cracking of biomass in co-pyrolysis, leading to higher gas and coke residue comparatively. The viscosity, density, and flash point of oil obtained in catalytic co-pyrolysis were significantly reduced. While the oil obtained from individual pyrolysis of algae is rich in phenolic derivatives, and that of PP, PE has aliphatic hydrocarbons, and EPS has monoaromatic hydrocarbons as major compounds. The synergistic role of plastic and biomass in co-pyrolysis was observed in the formation of products and oil composition. The bio-oil from catalytic co-pyrolysis is composed of aliphatic oxygenates, aliphatic hydrocarbons, cyclic aliphatic hydrocarbons, and phenolics. The chemicals and hydrocarbons present in the oil have a carbon number in the range of C6 to C30. An increase in carbon and hydrogen elemental composition was observed in bio-oil obtained from co-pyrolysis.