To maximize the electrochemical performance of a pseudocapacitor, we have holistically designed yolk–shell nanostructured electrode materials endowed with multiple electroactive redox states, fast redox kinetics and most importantly superior cycling stability. This can effectively be achieved by concoction of high surface area ultrathin mesoporous shell, volumetric buffering void space and lastly an in-built supporting framework that alleviates prevalent fracturing due to prolong cycling. Herein, a polystyrene spheres (PS) core known for its low-cost, lightweight, durability and elastoplasticity properties are explicitly introduced as a localized mechanical support to augment the susceptible ultrathin hollow structures. Unlike, conventional physical support which comes directly from a backbone scaffold such as foam, here the yolk–shell structure adopts comparative advantages of void spaces and movable cores needed not only for volumetric buffering but also to assume a self-supporting framework. The PS supported NiCo2S4 (PS@NiCo2S4) nanocolloids possess high surface area (220–266m2 g−1) and structural stability which manifested high capacitance and excellent cycling performances.