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In this paper, an estimation of the electricity generating potential as well as the environmental implications of bio-oil derivable from pyrolysis of plastic in some selected cities of Nigeria is conducted. The estimation premise on the experimental results obtained across different literatures, which gave the possible bio-oil yield of different mixture of plastics. First, the amount of plastic in different streams of municipal solid waste across the selected cities are sourced from the local literature and are used to estimate the theoretical amount of bio-oil obtainable through pyrolysis of plastics. Thereafter, the electricity generation potential of the bio-oil is estimated. The environmental impact assessment is conducted through the determination of its global warming and acidification impact. Some of the key results show that pyrolysis of plastic waste has great potential for electricity generation in Nigeria with total electricity generation potential of 87.5 MW with total global warming potential 634.9 kgCO(2) (i.e. 0.634922769 tCO(2)e) and acidification potential of 16.4 kgSO(2). The paper is important as it gives an insight into the probable opportunities in waste to energy technology for electricity generation using plastic wastes. This could be an eye-opener to the investors, researcher, policy makers, relevant government parastatals, and legislators.