Designing dual-functional electrode materials for supercapacitors and pollutant sensors has attracted great interest from researchers for urgent demand in green energy and the environment. In this work, a novel electrode material V2CTx@NiCoMn-OH was successfully constructed for dual-functional orientation via a two-step synthesis strategy, in which the NiCoMn-OH with a three-dimensional (3D) hollow structure was fabricated by employing ZIF-67 as a template and simple anion exchange and composited with the two-dimensional (2D) layered V2CTx MXene. The intercalation of NiCoMn-OH can effectively limit the self-accumulation of V2CTx MXene nanosheets and build a 3D cross-linked hollow structure, thereby broadening the ion transport channel, exposing more active sites of V2CTx@NiCoMn-OH, and simultaneously improving the conductivity of NiCoMn-OH. Benefiting from the unique 3D cross-linked hollow structure, the optimized V2CTx@NiCoMn-OH-20 electrode material exhibits an excellent specific capacitance of 827.45 C g−1 at 1 A g−1. Furthermore, the electrode material has excellent capacitance retention of 88.44% after 10,000 cycles. Moreover, the V2CTx@NiCoMn-OH-20//AC ASC device displays a high energy density of 88.35 Wh kg−1 as well as high power density of 7500 W kg−1 during operation. Additionally, the V2CTx@NiCoMn-OH-20 exhibited excellent electrocatalytic performance in the detection of hydroquinone, including the low detection limit of 0.559 μM (S/N = 3) and the wide linear range of 2–1050 μM. Therefore, the prepared V2CTx@NiCoMn-OH-20 has great potential applications in the fields of supercapacitors and hydroquinone sensors.