This paper presents a study of the combustion mechanism of hydrous and anhydrous ethanol in comparison to iso-octane and gasoline fuels in a single-cylinder spark-ignition research engine operated at 1000 rpm with 0.5 bar intake plenum pressure. The engine was equipped with optical access and tests were conducted with both Port Fuel Injection (PFI) and Direct Injection (DI) mixture preparation methods; all tests were conducted at stoichiometric conditions. The results showed that all alcohol fuels, both hydrous and anhydrous, burned faster than iso-octane and gasoline for both PFI and DI operation. The rate of combustion and peak cylinder pressure decreased with water content in ethanol for both modes of mixture preparation. Flame growth data were obtained by high-speed chemiluminescence imaging. These showed similar trends to the mass fraction burned curves obtained by in-cylinder heat release analysis for PFI operation; however, the trend with DI was not as consistent as with PFI. OH planar Laser induced fluorescence images were also acquired for identification of the local flame front structure of all tested fuels.