In this paper, the relationship between the reversible redox properties and the second-order nonlinear optical (NLO) responses for the title series of complexes has been systematically investigated by using the time-dependent density functional theory (TDDFT) method combined with the sum-over-states (SOS) formalism. The results reveal that the successive reduction processes of five PW11ReN redox states should be PW11ReVII (1) --> PW11ReVI (2) --> PW11ReV (3) --> PW11ReV1e ( 4) --> PW 11ReV2e (5). Furthermore, their electrochemical properties have been reproduced successfully. It is noteworthy that the second-order NLO behaviors can be switched by reversible redox for the present studied complexes. Full oxidation constitutes a convenient way to switch off the second-order polarizability (system 1). The incorporation of extra electrons causes significant enhancement in the second-order NLO activity, especially for the third reduced state (system 4), whose static second-order polarizability (betavec) is about 144 times larger than that of fully oxidized 1. The characteristic of the charge-transfer transition corresponding to the dominant contributions to the betavec values indicates that metal-centered redox processes influence the intramolecular donor or acceptor character. Therefore, these kinds of complexes with the facile and reversible redox states could become excellent switchable NLO materials.