In the urban area the internal combustion engines are the main source of CO₂, NO and particulate matter (PM) emissions. The reduction of these emissions is no more an option, but a necessity highlighted by the even stricter emission standards. In the last years, even more attention was paid to the alternative fuels. They allow both reducing the fuel consumption and the pollutant emissions. With regards to the gaseous fuels, methane is considered one of the most interesting in terms of engine application. It represents an immediate advantage over other hydrocarbon fuels because of the lower C/H ratio. In this paper the effect of the methane on the combustion process, the pollutant emissions and the engine performance was analyzed. The measurements were carried out in an optically accessible single-cylinder, Port Fuel Injection, four-stroke SI engine equipped with the cylinder head of a commercial 250 cc motorcycles engine and fuelled both with gasoline and methane. Optical measurements were performed to analyze the combustion process with a high spatial and temporal resolution. In particular, optical techniques based on 2D-digital imaging were used to follow the flame propagation in the combustion chamber. UV-visible spectroscopy allows detecting the chemical markers of combustion process such as the radicals OH and CH. The exhaust emissions were characterized by means of a gaseous analyzer and an opacimeter. The measurements were performed under steady state conditions, at 2000 rpm at minimum and full load.