Large eddy simulation (LES) of transient magnetohydrodynamic (MHD) turbulent flow under a single-ruler electromagnetic brake (EMBr) in a laboratory-scale, continuous-casting mold is presented. The influence of different electrically-conductive boundary conditions on the MHD flow and electromagnetic field was studied, considering two different wall boundary conditions: insulating and conducting. Both the transient and time-averaged horizontal velocities predicted by the LES model agree well with the measurements of the ultrasound Doppler velocimetry (UDV) probes. Q-criterion was used to visualize the characteristics of the three-dimensional turbulent eddy structure in the mold. The turbulent flow can be suppressed by both configurations of the experiment’s wall (electrically-insulated and conducting walls). The shedding of small-scale vortices due to the Kelvin–Helmholtz instability from the shear at the jet boundary was observed. For the electrically-insulated walls, the flow was more unstable and changed with low-frequency oscillations. However, the time interval of the changeover was flexible. For the electrically-conducting walls, the low-frequency oscillations of the jets were well suppressed; a stable double-roll flow pattern was generated. Electrically-conducting walls can dramatically increase the induced current density and electromagnetic force; hence they contribute to stabilizing the MHD turbulent flow.