We performed a combined study of the (001)-cleavage plane of lanthanum hexaboride (LaB6) using scanning tunneling microscopy (STM) and density functional theory (DFT). Experimentally, we found a (2×1) reconstructed surface on a local scale. The reconstruction is only short-range ordered and tends to order perpendicularly to step edges. At larger distances from surface steps, the reconstruction evolves to a labyrinth-like pattern. These findings are supported by low-energy electron diffraction (LEED) experiments. Slab calculations within the framework of DFT shows that the atomic structure consists of parallel lanthanum chains on top of boron octahedra. Scanning tunneling spectroscopy (STS) shows a prominent spectral feature at −0.6 eV. Using DFT, we identify this structure as a surface resonance of the (2×1) reconstructed LaB6 (100)-surface which is dominated by boron dangling bond-states and lanthanum d-states.