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The premixtures flufenacet plus diflufenican and flufenacet plus diflufenican plus metribuzin are two herbicides recently registered in Greece for weed control in bread wheat (<i>Triticum aestivum</i> L.) and barley (<i>Hordeum vulgare</i> L.) with application early post-emergence to the crop (1st–3rd leaf growth stage). To evaluate the selectivity of these new herbicides, pot experiments were conducted by applying flufenacet plus diflufenican at 240 + 120 g ai ha⁻¹ and flufenacet plus diflufenican plus metribuzin at 119.7 + 119.7 + 44.8 g ai ha⁻¹ to bread wheat and barley, at 1st (BBCH-11), 2nd (BBCH-12) and 3rd (BBCH-13) leaf growth stage. The efficacy of the herbicides at the above-mentioned rates in pre-emergence application was also tested on three ALS/ACCase herbicide-resistant populations of <i>Lolium rigidum</i> Gaudin in comparison with the pre-emergence herbicides prosulfocarb and chlorotoluron plus diflufenican at 3200 g ai ha⁻¹ and 1380 + 92 g ai ha⁻¹, respectively. The results revealed decreased selectivity of both premixtures when applied at BBCH-11 for both winter cereals, with flufenacet plus diflufenican being less selective compared to flufenacet plus diflufenican plus metribuzin. Both herbicides highly controlled the three herbicide-resistant <i>L. rigidum</i> populations. The results indicated that both premixtures are effective chemical options for the management of herbicide resistant <i>L. rigidum</i>. To ensure crop safety and optimize efficacy, application at BBCH-12 is recommended.