A population of rigid ryegrass (Lolium rigidum Gaudin) from a field on the Eyre Peninsula, South Australia, was suspected of resistance to thiocarbamate herbicides. Dose–response studies were conducted on this population (EP162) and two susceptible populations (SLR4 and VLR1). The resistant population exhibited cross-resistance to triallate, prosulfocarb, EPTC, and thiobencarb with higher LD50 to triallate (14.9-fold), prosulfocarb (9.4-fold), EPTC (9.7-fold), and thiobencarb (13.6-fold) compared with the susceptible populations SLR4 and VLR1. The resistant population also displayed resistance to trifluralin, pyroxasulfone, and propyzamide. The LD50 of the resistant population was higher for trifluralin (13.8-fold), pyroxasulfone (8.1-fold), and propyzamide (2.7-fold) compared with the susceptible populations. This study documents the first case of field-evolved resistance to thiocarbamate herbicides in L. rigidum.