We investigate the spin dynamics, starting from the initial band-insulating state, of fermionic high-spin atoms in optical superlattices. Through numerical simulations and analytical calculations, we determine the time evolution behavior of the system. When the spin-changing strength and tunneling strength are comparable, the spin dynamics feature a spin-changing oscillation with the amplitude modulated by the superexchange interaction. When the double-well potential is very shallow, the spin dynamics feature a simple harmonic oscillation with the oscillation frequencies related only to the spin-changing strength, which can be properly explained with the perturbation model.