Black phosphorus (BP) allotrope has an orthorhombic crystal structure with a narrow bandgap of 0.35 eV. This material is promising for 2D technology since it can be exfoliated down to one single layer: the well-known phosphorene. In this work, bulk BP was synthesized under high-pressure conditions at high temperatures. A detailed structural investigation using neutron and synchrotron X-ray diffraction revealed the occurrence of anisotropic strain effects on the BP lattice; the combination of both sets of diffraction data allowed visualization of the lone electron pair 3s 2 . Temperature-dependent neutron diffraction data collected at low temperature showed that the a axis (zigzag) exhibits a quasi-temperature-independent thermal expansion in the temperature interval from 20 up to 150 K. These results may be a key to address the anomalous behavior in electrical resistivity near 150 K. Thermoelectric properties were also provided; low thermal conductivity from 14 down to 6 Wm −1 K −1 in the range 323−673 K was recorded in our polycrystalline BP, which is below the reported values for singlecrystals in literature.