Premixed charge compression ignition (PCCI) has been shown to be a promising strategy to simultaneously reduce emissions while realizing improved fuel economy. PCCI combustion uses high levels of pre-combustion mixing to lower both NOx and soot emissions by ensuring low equivalence ratio and low flame temperatures. The high level of pre-combustion mixing results in a primarily kinetics controlled combustion process.In this work, optical diagnostics have been applied in a transparent DI diesel engine equipped with the head of Euro5 commercial engine and the last generation CR injection system. In order to realize the PCCI combustion the injection of neat ethanol has been performed in the intake manifold. The engine run in continuous way at 1500 rpm engine speed and commercial diesel fuel has been injected into the cylinder. The PCCI combustion has been analyzed by means of UV- Visible digital imaging and the mixing process, the autoignition of the charge have been investigated. In particular, the bulk combustion characteristics in terms of in-cylinder pressure, as well as the species like OH, HCO, and CH, involved in the autoignition process have been detected and the in-cylinder air/fuel ratio has been determined.