The (e, 2e) triple-differential cross sections of Ag + (4p, 4s) are calculated based on the three-body distorted-wave Born approximation considering post-collision interaction in coplanar symmetric geometry. The energy of the outgoing electron is set to be 50, 70, 100, 200, 300, 500, 700, and 1000 eV, and the intensity and splitting of forward and backward peaks are discussed in detail. Some new structures are observed around 15 • and 85 • for 4p and 4s orbitals. Structures in triple-differential cross sections at 15 • are reported for the first time. A double-binary collision is proposed to explain the formation of such structures. The structures at 85 • are also considered as the result of one kind of double-binary collision.