Van der Waals heterostructures with incommensurate contact interfaces show excellent tribological performance, which provides solutions for the development of new solid lubricants. In this paper, a facile electrostatic layer-by-layer self-assembly (LBL) technique was proposed to prepare multi-layer van der Waals heterostructures tungsten disulfide/hexagonal boron nitride (vdWH WS 2/h-BN). The h-BN and WS 2 were modified with poly (diallyldimethylammonium chloride) (PDDA) and sodium dodecyl benzene sulfonate (SDBS) to obtain the positively charged PDDA@h-BN and the negatively charged SDBS@WS 2, respectively. When the mass ratio of PDDA to h-BN and SDBS to WS 2 were both 1:1 and the pH was 3, the zeta potential of PDDA@h-BN and SDBS@WS 2 were 60.0 mV and −50.1 mV, respectively. Under the electrostatic interaction, the PDDA@h-BN and SDBS@WS 2 attracted each other and stacked alternately along the (002) crystal plane forming the multi-layer (four-layer) vdWH WS 2/h-BN. The addition of the multi-layer vdWH WS 2/h-BN (1.0 wt%) to the base oil resulted in a significant reduction of 33.8% in the friction coefficient (0.104) and 16.8% in the wear rate (4.43 × 10 −5 mm 3/(N·m)). The excellent tribological property of the multi-layer vdWH WS 2/h-BN arose from the lattice mismatch (26.0%), a 15-fold higher interlayer slip possibility, and the formation of transfer film at the contact interface. This study provided an easily accessible method for the multi-layer vdWH with excellent tribological properties.