PIXE spectra were recorded with the aid of a crystal monochromator. The most prominent change of the X-ray spectra with fine structure was observed on the intensity distributions of satellite lines emitted from atoms embedded in different chemical environments. As the origin of such a change in the satellite structures, two fundamental causes can be considered. The first one is change in the ionization cross section of the atom of interest for the multiply ionized states. The second is reconstruction of the molecular orbitals, especially in the outermost electronic shell, after an inner-shell ionization but before a characteristic X-ray emission. PIXE is promising for studying bond natures of atoms, as well as for microanalysis.