Due to its potential for simultaneous improvement in fuel consumption and exhaust emissions, controlled autoignition (CAI) combustion has been subject to continuous research in the last several years. At the same time, there has been a lot of interest in the use of alternative fuels in order to reduce reliance on conventional fossil fuels. Therefore, this experimental study has been carried out to investigate the effect of alcohol fuels on the CAI combustion process and on the resulting engine performance. The experimental work was conducted on an optical single cylinder engine with an air-assisted injector. To achieve controlled autoignition, residual gas was trapped in the cylinder by using negative valve overlap and an intake air heater was used to ensure stable CAI combustion in the optical engine. Methanol, ethanol and blended fuels were tested and compared with the results of gasoline. The combustion processes were analysed through total chemiluminescence images captured with a high speed camera equipped with an intensifier. In addition, the effect of spark discharge was investigated. The images show that CAI combustion of alcohol fuels was characterized with fast and early autoignition combustion compared with pure gasoline. Chemiluminescence of the gasoline fuel was most visible and it decreased with increasing percentage of oxygenated fuels. During the re-compression stroke, chemiluminescence images of the gasoline engine indicated the presence of oxidation reactions. In the presence of spark discharge, the location of charge ignition was dominated by spark discharge at the center of cylinder while simultaneous autoignition sites were found around the periphery of the combustion chamber for non-spark-assisted ignition.