In the last years, even more attention was paid to the alternative fuels which can allow both reducing the fuel consumption and the pollutant emissions. Among gaseous fuels, methane is considered one of the most interesting in terms of engine application. It represents an immediate advantage over other hydrocarbon fuels leading to lower CO₂ emissions; if compared to gasoline, CH₄ has wider flammable limits and better anti-knock properties, but lower flame speed. The addition of H₂ to CH₄ can improve the already good qualities of methane and compensate its weak points. In this paper a comparison was carried out between CH₄ and different CH₄/H₂ mixtures. The measurements were carried out in an optically accessible small single-cylinder, Port Fuel Injection spark ignition (PFI SI), four-stroke engine. It was equipped with the cylinder head of a commercial 250 cc motorcycle engine representative of the most popular two-wheel vehicles in Europe. Optical measurements were performed to analyze the combustion process with 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 gaseous analyzers. The measurements were performed under steady state conditions at different engine speed in order to evaluate the interaction of turbulence with the kernel and the interaction with the local flame. All the results highlight the combustion promotion due to the hydrogen addition.