Developing electrode materials with rational structures is an important strategy for constructing high-performance hybrid supercapacitors (HSCs). Herein, designing a yolk@shell structure composed of layered nickel-cobalt hydroxide with a Ni/Co feed ratio of 4:1 (denoted as layered Ni4Co1 hydroxide) and nickel-cobalt sulfide with a sulfuration duration of 2 h (labeled as Ni4Co1S-2h) to enhance the capacity and stabilize the cyclic performances of HSCs was conducted. The yolk@shell structured microspheres of layered Ni4Co1 hydroxide were synthesized using a cetyltriethylammonium bromide (CTAB) template-assisted solvothermal treatment. Subsequently, nickel-cobalt sulfide microspheres with the unique yolk@shell structure were prepared from layered Ni4Co1 hydroxide precursor. Notably, yolk@shell Ni4Co1S-2h microspheres feature a large specific surface area and an interspace between the yolk and shell, facilitating charge transfer but also effectively alleviating volume expansion during ion transport and electron transfer. The resultant Ni4Co1S-2h material demonstrates a superior capacity of 902.2 C·g−1 at 3·A g−1, while the assembled Ni4Co1S-2h//porous carbon (PC) HSC shows a relatively higher energy density (83.1 Wh·kg−1) and power density (15000 W·kg−1). The design of yolk@shell structured layered Ni4Co1 hydroxide and Ni4Co1S-2h electrode materials holds significant implications for the advancement of high-performance HSCs.