The exploitation of two-dimensional (2D) vanadium carbide (V₂CT_x, denoted as V₂C) in electrocatalytic hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR) is still in the stage of theoretical study with limited experimental exploration. Here, we present the experimental studies of V₂C MXene-based materials containing two different bismuth compounds to confirm the possibility of using V₂C as a potential electrocatalyst for HER and NRR. In this context, for the first time, we employed two different methods to synthesize 2D/0D and 2D/2D nanostructures. The 2D/2D V₂C/BVO consisted of BiVO₄ (denoted BVO) nanosheets wrapped in layers of V₂C which were synthesized by a facile hydrothermal method, whereas the 2D/0D V₂C/Bi consisted of spherical particles of Bi (Bi NPs) anchored on V₂C MXenes using the solid-state annealing method. The resultant V₂C/BVO catalyst was proven to be beneficial for HER in 0.5 M H₂SO₄ compared to pristine V₂C. We demonstrated that the 2D/2D V₂C/BVO structure can favor the higher specific surface area, exposure of more accessible catalytic active sites, and promote electron transfer which can be responsible for optimizing the HER activity. Moreover, V₂C/BVO has superior stability in an acidic environment. Whilst we observed that the 2D/0D V₂C/Bi could be highly efficient for electrocatalytic NRR purposes. Our results show that the ammonia (NH₃) production and faradaic efficiency (FE) of V₂C/Bi can reach 88.6 μg h⁻¹ cm⁻² and 8% at −0.5 V vs. RHE, respectively. Also V₂C/Bi exhibited excellent long-term stability. These achievements present a high performance in terms of the highest generated NH₃ compared to recent investigations of MXenes-based electrocatalysts. Such excellent NRR of V₂C/Bi activity can be attributed to the effective suppression of HER which is the main competitive reaction of the NRR.