We propose and demonstrate an electro-optical chaotic communication system with additional chaotic phase-shift based on the mutual coupling structure. Under the condition of complete concealment of time-delayed signatures (TDSs), the key space of the system is greatly enhanced and highly reliable chaotic communication is finally realized. The additional-phase introduced by the new branch is nonlinearly superimposed on the phase generated by the chaotic signal of the original branch, which improves the complexity and aperiodicity of chaos. For security performance, the system only needs a very small feedback gain (i.e., β_i = 2.5) to conceal TDSs. Moreover, since the system has only one chaotic signal transmitted in the transmission link, it overcomes the exposure of TDSs caused by the cross-correlation characteristics between different links. At the same time, the system has strong synchronization robustness and can achieve high-quality communication when the parameters are well-matched. To sum up, the proposed system can effectively resist eavesdropping, which provides security for the physical layer of optical networks.