The siliconization of pharmaceutical glass containers is an industrially frequently applied procedure. It is done by spreading an aqueous silicone oil emulsion film on the inner surface and successive heat curing treatment at temperatures above 300 degrees C for 10-30 min. It was often proposed that a covalent bonding of PDMS to the glass or branching of the linear PDMS occurs during heat treatment. The present study was performed for a detailed investigation of the glass and silicone (polydimethylsiloxane = PDMS) chemical state before and after heat-curing treatment and analysis of the bond nature. Combined X-ray excited photoelectron (XPS) and Auger electron spectroscopy as well as angle resolved XPS-measurements were used for analysis of the glass samples. The silicon surface atoms of the borosilicate container glass were transformed to a quartz-like compound whereas the former linear PDMS had a branched, two-dimensional structure after the heat curing treatment. It was concluded that the branching indicates the formation of new siloxane bonds to the glass surface via hydroxyl groups. Further evidence for the presence of bonded PDMS at the glass surface can be found in the valence band spectra of the siliconized and untreated samples. However, this bond could not be detected directly due to its very similar nature to the siloxane bonds of the glass matrix and the organosilicon backbone of PDMS. Due to the high variation of data from the siliconized samples it was concluded, that the silicone film is not homogeneous. Previously raised theories of reactions during heat-curing glass siliconization are supported by the XPS data of this investigation. Yet, the postulation of fixing or baking the silicone on the glass surface is only partially true since the bonded layer is very thin and most of the silicone originally on the surface after heat curing can be removed by suitable solvents. This fraction can therefore still interact with drug products being in contact to the siliconized container wall.