The crystallographic structure of La0.7Ca0.3MnO3 (LCMO) ultra-thin films grown on SrTiO3(001) has been investigated by surface X-ray diffraction (SXD) and the correlation between their transport and magnetic properties and crystallographic structure is discussed. LCMO thin films in a thickness range between 2.4 and 27 run were grown by DC-sputtering on SrTiO3(001). We distinguish two different crystallographic structures associated to the 2.4 and 27 nm thin films, respectively. The 27 nm film structure corresponds to a tetragonal perovskite (space group Pbnm), as has been reported for bulk LCMO. For the 2.4 nm film the La/Ca ions are located at the regular position of an ideal perovskite and the MnO6 octahedrons are aligned along the c-axis. The MnO2 stacking layer (basal plane) is distorted and coplanar to the a-b crystallographic axis with an anti-correlation between octahedron layers. This observed distortion is not compatible with the Pbnm space group. The new phase, which cannot be excluded to coexist at the interface of thicker films, can be described, as an example, through an 14/mcm or Pbcn space group. Based on the observed structure, plausible models to explain their transport and magnetic behaviour are proposed. For the 2.4 nm film, an octahedron in-plane (basal plane) distortion induced by the substrate is observed. Thicker films behave structurally and magnetically as bulk-like materials. (C) 2004 Elsevier B.V. All rights reserved.