Ni- and Fe-based metal-organic frameworks (NiFe-MOFs) have abundant valence states and have the potential to be used as bifunctional electrode materials. However, unannealed NiFe-MOFs are still not widely used in electrode materials, including electrochemical sensing, supercapacitors, and overall water splitting. In addition, the direct growth of active material on a conductive carrier has been developed as a binder-free strategy for electrode preparation. This strategy avoids the use of insulating binders and additional electrode treatments, simplifies the preparation process of the NiFe-MOFs, and improves the conductivity and mechanical stability of the electrode. Therefore, in this study, we employed a simple solvothermal method combined with an in situ growth technique to directly grow NiFe-MOF-X (X = 4, 8, 12) nanomaterials of different sizes and morphologies on nickel foam at low reaction temperatures and different reaction times. The NiFe-MOF-8 electrode exhibited high capacitive properties, with an area-specific capacitance of 5964 mF cm−2 at 2 mA cm−2 and excellent durability. On the other hand, NiFe-MOF-12 exhibited strong catalytic activity in electrocatalytic tests performed in a 1 M KOH aqueous solution, demonstrating hydrogen evolution reaction (η10 = 150 mV) and oxygen evolution reaction (η50 = 362 mV) activities. The electrochemical sensing tests demonstrated a good response to BPA. Overall, our results suggest that the direct growth of NiFe-MOFs on nickel foam using a simple solvothermal method combined with an in situ growth technique is a promising strategy.