Phase constitution, microstructure, and mechanical properties of the as-cast and homogenized CrCuFeNiV multi principalelement alloys were investigated. Results show that the microstructures of CrCuFeNiV alloys either in the as-cast orhomogenized state were constituted by the dispersed Cu-rich fcc regions and the matrix regions (intertwined bcc + σ phases). Thereinto, the σ phase, ranged from nanometers to microns, was a complex multicomponent intermediate phase with a highsolubility for Fe, Cr, Ni, and V. This phase structure and hardness had an impressive thermal stability, which was evidencedby the current annealing treatment. High hardness (822 HV and 793 HV) was simultaneously achieved under an appliedload of 200 g in the as-cast and homogenized CrCuFeNiV alloys, on account of the incorporation of the high-stiffness σphase against the fcc and bcc phases. The ultimate compressive strength of ~ 1490 MPa was obtained in the as-cast alloydue to the high deformation resistance to the dislocation movement of bcc phase and precipitation strengthening of σ phaseat the expense of plasticity. The deterioration in plasticity was attributed to the stress concentration easily triggered by thehard and brittle σ phase.