In principle, the plasma nitriding of Al based substrates is a well-known process, though it remains extremely challenging from both the technological point of view and the aspect of stress loading conditions. In order to improve the latter, a duplex treatment consisting of plasma nitriding and subsequent surface remelting using electron beam technology was employed. The focus of this paper (part I) was on the characterisation of the initial microstructure after plasma nitriding. This should create the basis for a better understanding of the processes taking place or changes in the subsequent duplex treatment. This was done with the help of high-resolution imaging and analysis tools in the scanning and transmission electron microscope as well as XPS analyses. Special attention was paid to the nitriding mechanism at the interface as a function of the local microstructural constituents of the hypereutectic Al alloy substrate (Al solid solution, primary silicon, and intermetallic phases). While the main part of the nitride layer formed consisted of AlN and small fractions of pure Al in the diffusion paths, other nitrides and oxides could also be detected in the area of the interface.