The finite-temperature entanglement entropy for an alternating spin-1/2 chain with multi-spin interactions is investigated by means of Green’s function theory combined with Jordan-Wigner transformation, to identify the spin-Peierls (SP) transition. It is found that the two-site thermal entanglement entropy is a useful tool to characterize theSPtransition. In addition, the competition between multi-spin interaction and Peierls-dimerization plays a central role in the critical phenomenon of the system.