The electronic, phonon and thermoelectric transport properties of (PbTe)2 layer are systematically investigated by using first-principles pseudopotential method and Boltzmann transport equation. Our calculations demonstrate that there is a valley degeneracy of six for the top valence band, which leads to larger carrier concentration and thus higher electrical conductivity without obvious reduction in the Seebeck coefficient. Moreover, the intrinsic van der Waals interactions between neighboring Pb layers induce additional phonon scattering and thus ultrasmall lattice thermal conductivity. As a consequence, a maximum p-type ZT value of 2.9 can be achieved at 1000 K. Moreover, we find almost identical n- and p-type ZT in the temperature range from 300 K to 800 K.