By treating mer, trans-Re(${equiv}NC_6H_5)(PPh_3)_2Cl_3$, Ⅰ, with 5 atm of CO at room temperature for 52 h, fac-Re(${equiv}NC_6H_5)(CO)(PPh_3)Cl_3$, Ⅱ, was obtained as dark green precipitates in 81% yield. The crystal structure of Ⅱ was determined through X-ray diffraction. Ⅱ crystallizes in the monoclinic system, space group $P2_1/n$ with cell parameters a=9.740 (2) ${AA}$, b=16.210 (5) ${AA}$, c=16.192 (6) ${AA}$, ${eta}$=97.50 $(2)^{circ}$, and Z=4. Least-squares refinement of the structure led to a R$(R_w)$ factor of 0.030 (0.036) for 2878 unique reflections of I>3${sigma}(I)$ and for 241 variables. In comparison to the starting material Ⅰ, the bond distance of Re-N became longer from 1.726 (6) to 1.736 (5) ${AA}$ and the bond angle of Re-N-C(Ph) became smaller from 172.6 (6) to 167.0 $(2)^{circ}$, indicating that the Re-N bond in Ⅱ is weakened and has a less triple-bond character than that in Ⅰ.