The electronic structures of epitaxially grown films of Ti 3 AlC 2 , Ti 3 SiC 2 , and Ti 3 GeC 2 have been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured high-resolution Ti L , C K , Al L , Si L , and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L emission of Ti 3 AlC 2 . As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si layers, strongly hybridized spectral shapes are detected in Ti 3 AlC 2 and Ti 3 SiC 2 , respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.