Spectro-polarimetric observations with the Solar Optical Telescope onboard Hinode reveal the emission spectrum of the Fe I 630 nm lines at the solar limb. The emission shell extends for less than 1'' thereby making it extremely difficult to detect from ground-based observatories viewing the limb through the Earth's atmosphere. The linear polarization signal is clearly due to scattering and it is predominantly oriented in the radial direction. Using a comprehensive atomic model of iron, we are able to interpret qualitatively the observed signals, including the radial orientation of the linear polarization. The Hanle effect causes the linear polarization of the Fe I 630 nm lines to be sensitive to magnetic fields between ~0.1 G and ~40 G, and also to be sensitive to the field's topology for stronger fields. The overall degree of observed polarization can be reproduced by randomly oriented horizontal magnetic fields of strength ≈2 G. The discovery of their scattering polarization signals thus opens a new diagnostic opportunity for these lines.