Achieving high network traffic demand in limited spectrum resources is a technical challenge for the beyond 5G and 6G communication systems. To this end, ambient backscatter communication (AmBC) is proposed for Internet-of-Things (IoT), because the backscatter device (BD) can realize communication without occupying extra spectrum resources. Moreover, the spectral efficiency can be further improved by using two-way (TW) communication. However, secure communication is a great challenge for accessing massive IoT devices due to the broadcasting nature of wireless propagation environments. In light of this fact, this article proposed a two-way ambient backscatter communication (TW-AmBC) network with an eavesdropper. Specifically, the physical layer security (PLS) is studied through deriving the analytical/asymptotic expressions of the outage probability (OP) and intercept probability (IP). Moreover, the outage probabilities (OPs) in high signal-to-noise ratio (SNR) regions are studied for the asymptotic behavior and the intercept probabilities (IPs) in high main-to-eavesdropping ratio (MER) regions as well. Through analysis and evaluation of simulation performance, the results show that (i) when considering the target node, the OP of the BD decreases with increasing SNR, that is, enhancing the reliability; (ii) an optimal value of BD’s reflection coefficient that maximize the reliability of backscatter link can be obtained; (iii) in high SNR regions, the OPs approach a constant; thus, the diversity orders are zero; (iv) when increasing the MER, the IP of target node decreases, suggesting the security enhances; (v) a trade-off exists between reliability and security which can be optimized by carefully designing the parameters.