We report the electronic properties of the metallic PdSn2 single crystals by means of electrical resistivity, Hall effect, angle-resolved photoemission spectroscopy (ARPES) measurements and band-structure calculations. A simultaneous two-band analysis is conducted on magnetoresistance (MR) and Hall effect data, revealing hole-carrier dominated transport behavior. ARPES results clearly indicate the multiband nature of PdSn2 with the presence of shallow hole and electron pockets at the Fermi level, supported by first-principles calculations. From the MR data, a breakdown of Kohler's rule in the 300–80 K range is observed. We consider a possible explanation for this phenomenon, which is associated with the temperature-induced band shift near the Fermi surface.