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In this paper, we introduce one family of vectorial prolate spheroidal wave functions of real order $α>-1$ on the unit ball in $R^3$, which satisfy the divergence free constraint, thus are termed as divergence free vectorial ball PSWFs. They are vectorial eigenfunctions of an integral operator related to the finite Fourier transform, and solve the divergence free constrained maximum concentration problem in three dimensions, i.e., to what extent can the total energy of a band-limited divergence free vectorial function be concentrated on the unit ball? Interestingly, any optimally concentrated divergence free vectorial functions, when represented in series in vector spherical harmonics, shall be also concentrated in one of the three vectorial spherical harmonics modes. Moreover, divergence free ball PSWFs are exactly the vectorial eigenfunctions of the second order Sturm-Liouville differential operator which defines the scalar ball PSWFs. Indeed, the divergence free vectorial ball PSWFs possess a simple and close relation with the scalar ball PSWFs such that they share the same merits. Simultaneously, it turns out that the divergence free ball PSWFs solve another second order Sturm-Liouville eigen equation defined through the curl operator $\nabla\times $ instead of the gradient operator $\nabla$.