Metal oxide semiconductors, known for their exceptional optical transparency, high carrier mobility, and stability, have found extensive use in emerging technologies such as optoelectronics and energy storage devices. Among all metal oxide semiconductors, nickel oxide (NiO) stands out as a highly favorable candidate due to its p‐type conductivity along with its substantial band gap (3.5–4 eV) for the broad range of applications, including gas sensors, high‐rate Lithium‐ion batteries, high‐performance supercapacitors, and photovoltaic devices. In light of these versatile applications, our current study presents a comprehensive comparative analysis of the structural and optoelectronic properties of NiO and potassium (K)‐doped NiO nanocrystals. The nanocrystals were synthesized using the co‐precipitation route and subsequently annealed at 500°C under ambient conditions. The effect of K doping on the structural and optoelectronic characteristics was systematically examined using various techniques, including x‐ray diffraction, UV–visible spectroscopy, Raman spectroscopy, and Hall effect measurements. To explore the structural characteristics, XRD measurements were performed, which confirm the FCC structure of nanocrystals. The optical property analysis suggested that the formation of the energy level can contribute to reduction of the band gap. A sharp peak at 397 cm−1 is associated with NiO bond in FTIR spectra which verifies the formation of nanocrystals. Moreover, the incorporation of K increases the intensity of the Raman peaks, which provides evidence for the higher degree of crystallinity in doped samples. These results of Raman scattering are in good agreement with XRD outcomes. In addition, the resistivity of NiO nanocrystals decreases monotonically with the increasing K concentration. The results of temperature‐dependent resistivity further demonstrate that electrons required more energy to jump from one polaron state to another in the case of x = 0.01 M and 0.03 M doped Ni0.5‐xKxO samples. The combination of a diminished band gap and enhanced conductivity makes these materials exceptionally promising for applications in optoelectronics and energy storage.