Many 2D few-layer materials show piezoelectric or pyroelectric effects due to the loss-of-inversion symmetry induced by broken structure, although they are not piezoelectric or pyroelectric in the bulk. In this work, we find that the puckered graphene-like 2D few-layer black phosphorene is pyroelectric and shows a pyro-catalytic effect, where the pyroelectric charges generated under ambient cold-hot alternation are utilized for hydrogen evolution and dye molecule decomposition. Under thermal cycling between 15 °C and 65 °C, the 2D few-layer black phosphorene shows a direct hydrogen generation of about 540 μmol per gram of catalyst after 24 thermal cycles and about 99% decomposition of Rhodamine B dye after 5 thermal cycles. This work opens a door for the pyro-catalytic energy harvesting from the cold-hot alternations by a class of 2D few-layer materials.