Ultracold atoms in optical lattices hold promise for the creation of entangled states for quantum technologies. Here we report on the generation, manipulation and detection of atomic spin entanglement in an optical superlattice. Using a spin-dependent superlattice, atomic spins in the left or right sites can be individually addressed and coherently manipulated with near-unity fidelities by microwave pulses. The spin entanglement of the two atoms in the double wells of the superlattice is generated via the dynamical evolution governed by spin superexchange. By monitoring the collisional atom loss with in situ absorption imaging we measure the spin correlations of the atoms inside the double wells and obtain a lower bound on the entanglement fidelity of 0.790.06, and a violation of a Bell’s inequality SD2.210.08.