Near-edge x-ray absorption fine structure (NEXAFS) is used to examine the chemical bonding in boron and boron-nitride films sputter deposited from a fully-dense, pure boron target. Reactive sputtering is used to prepare the boron-nitride and multilayered films. Although the process of sputter deposition often produces films that lack long range order, NEXAFS reveals the distinguishing features of sp
2 and sp
3 hybridization that are associated with different crystalline structures. The sensitivity of NEXAFS to local order further provides details in bonding modifications that exist in these films.