This paper deals with the numerical analysis of the particle inertia and volume fraction effects on colliding particle-pair velocity correlation immersed in an unsteady isotropic homogeneous turbulent flow. Such correlation function is required to build reliable statistical models for inter-particle collisions, in the frame of the Euler–Lagrange approach, to be used in a broad range of two-phase flow applications. Computations of the turbulent flow have been carried out by means of Direct Numerical Simulation (DNS) by the Lattice Boltzmann Method (LBM). Moreover, the dependence of statistical properties of collisions on particle inertia and volumetric fraction is evaluated and quantified. It has been found that collision locations of particles of intermediate inertia, StK~1, occurs in regions where the fluid strain rate and dissipation are higher than the corresponding averaged values at particle positions. Connected with this fact, the average kinetic energy of colliding particles of intermediate inertia (i.e., Stokes number around 1) is lower than the value averaged over all particles. From the study of the particle-pair velocity correlation, it has been demonstrated that the colliding particle-pair velocity correlation function cannot be approximated by the Eulerian particle-pair correlation, obtained by theoretical approaches, as particle separation tends to zero, a fact related with the larger values of the relative radial velocity between colliding particles.