The effect of varying temperatures (15, 35, and 45 °C) on the corrosion behavior of a new single-phase distorted face-centered cubic (fcc) Al2Cr5Cu5Fe53Ni35 multi-principal element alloy (MPEA) was studied in simulated soil environments (NS4 solution). X-ray diffraction and electron backscattered diffraction were used to confirm the presence of a single phase throughout the microstructure. Electrochemical tests such as electrochemical impedance spectroscopy and linear polarization resistance were performed to evaluate the interfacial behavior and corrosion rate at various test conditions. Additionally, cyclic potentiodynamic polarization (CPP) tests were also carried out at the selected temperatures to study the pitting behavior of the MPEA. Surface characterization techniques such as X-ray photoelectron spectroscopy and scanning electron microscopy were used to identify the nature of the passive film formed in such complex materials as well as study the pitting characteristics after CPP testing. A stable passive film was found to be present all tested temperatures with the absence of preferential sites for pitting due to homogenous element distribution.