This study examines the possibility to provide control over ignition timing in a homogeneous charge compression ignition engine (HCCI) using a fuel additive whose molecular structure can be adapted upon exposure to UV light. The UV adapted molecule has a greater influence on retarding ignition than the original molecule, hence the ignition time can be modulated upon expose to UV light. The new fuel is referred to as a ‘smart fuel’. The fuel additive is in the form of 1,3-cyclohexadiene (CHD), upon UV exposure it undergoes electro-cyclic ring opening to form 1,3,5-hexatriene (HT). Various solutions of iso-octane, n-heptane and CHD have been irradiated by UV light for different amounts of time. CHD to HT conversion was examined using gas chromatography coupled with mass spectrometry. A primary reference fuel (PRF) mixture of 90% iso-octane and 10% n-heptane was used as a baseline in an optically accessible combustion chamber in a large bore, single cylinder compression ignition engine. The engine was operated in HCCI mode, using early injection to provide homogeneous mixture and utilized heated and compressed air intake. Following this a PRF with 5% CHD was used in the engine. A PRF with 5% CHD was then irradiated with UV light for 240 min, resulting in a PRF mixture containing 1.72% HT, this was then used in the engine. The HT containing PRF had a much later start of combustion compared with the CHD containing PRF, which in turn had a later start of combustion compared with the PRF baseline. This study has successfully validated the concept of using a photo-chemical ‘smart’ fuel to significantly change the ignition quality of a fuel in HCCI mode combustion and demonstrated the concept of on-board ‘smart fuel’ applications for ICE.