In Pr3Pd20Ge6, the Pr ions are located at two different crystallographic sites, 4a and 8c site. Antiferro-quadrupole ordering (AFQ) of the 8c site occurs at 250 mK. Ac susceptibility measurement indicated that antiferromagnetic ordering (AFM) of the 4a site and Hyperfine-enhanced Pr nuclear magnetic ordering of the 8c site occur at 77 and 9 mK, respectively. To clarify the magnetic and quadrupole properties of Pr3Pd20Ge6, thermal expansion and magnetostriction measurements on single crystal sample were carried out along the 001 direction up to 8 T down to 500 μK using a capacitive dilatometer. In zero field, relative length change ΔL/L in 001 direction had a dip at AFQ and abrupt decrease at AFM ordering. From thermal expansion and isothermal magnetostriction measurements, magnetic phase diagram of Pr3Pd20Ge6 along 001 direction was obtained.