Nitrogen K-shell near-edge X-ray absorption fine structure (NEXAFS) measurements have been used for the first time to demonstrate 1D alignment of cobalt phthalocyanine (CoPc) molecules inside carbon nanotubes (see figure), revealing a stacking order consistent with the metastable alpha-CoPc phase. In addition, transmission electron microscopy images show pristine nanotubes surfaces and near-optimal filling. The smallest internal diameter to host CoPc molecules is found to be 15 angstrom.