RS-485 MODBUS connection can be perfectly eavesdropped with RS-485 adapter and PC, much easier than RS-232 MODBUS which needs two RX ports to monitor master and slave simultaneously.
Just take care that the RS-485 adapter stays passive, TX-enable should be never activated.
You didn't tell about the RS-485 interfaces in your MODBUS setup, and how transmitters are enabled. A "popular" fault is however lack of pull-up and pull-down resistors that set the RS-485 idle level.