We report on enhanced mechanical, tribological, and surface-wettability characteristics of polymeric films dispersed with inorganic fullerene (IF)-type tungsten disulfide (WS2) nanoparticles derived through a two-step hydrothermal route. Imaging through transmission electron microscopy suggests the occurrence of polyhedral cage-like structures with a visibly nonspherical hollow ranging 55–75 nm. The mechanical stability of IF-type WS2 dispersed in polyvinyl alcohol (PVA) gets improved with increasing nano-inclusions, and upto 6 wt% loading. As compared with nanosheets, the IF-WS2 in PVA at the critical loading offers nearly 28.6, 33.6, and 42% respective improvements as regards, breaking stress, elongation at break, and toughness. Moreover, Stribeck curves in the mixed lubricating regime have revealed a nearly ∼80% reduction of coefficient of friction (COF) due to inclusion of IF-type WS2 in PVA. In the hydrodynamic region, the COF is drastically lowered from a typical value of 0.55 to 0.15 at the maximal sliding velocity with nanoparticle loading and despite the fact that the tribo feature gives a rising trend for a particular curve. Furthermore, exhibiting a progressive increase in water contact angle, a clear transition from the hydrophilic (∼64°) to hydrophobic (∼107°) surface of the nanocomposite films has been witnessed after inclusion of nano IF-WS2. An increased hydrophobicity and lowered surface adhesion and COF values along with marginal drop in surface energy are ensured in the investigated specimens. Investigation of responsive tribological and wetting–dewetting transition would find scope not only in coating and textile industry but also in smart miniaturized components.