Herbicide control of invasive plant species is generally efficient. However, there is a likelihood of the excessive application of non-selective herbicides that kill co-occurring native species and cause environmental toxicity. We present a case study on the control of the invasive exotic Solidago canadensis with photosynthetically active leaves in winter by applying glyphosate. This approach improves herbicide control efficiency, while preventing harm to most co-occurring native plants. We quantified the winter leaf phenology and photosynthetic capacity of S. canadensis and two commonly co-occurring native species. We tested the effects of glyphosate and competition on S. canadensis and native Imperata cylindrica with contrasting winter leaf phenology in both pot and field experiments. Finally, we surveyed the life forms and winter leaf phenology of most co-occurring plant species in eastern China to determine whether most co-occurring species and S. canadensis differ in winter leaf phenology. Old leaves withered much later and new leaves developed much earlier in S. canadensis than in the two co-occurring species. Both the old and new leaves of S. canadensis had high photosynthetic capacity in winter. In summer, glyphosate suppressed the growth of S. canadensis by 20.1–59.5% and growth of I. cylindrica to a greater extent (by 57.6–91.7%), whereas winter application of glyphosate at a certain concentration suppressed the growth of S. canadensis by 91.4–95.6% (the efficiency was higher than summer application), but had no impact on I. cylindrica. Glyphosate application in winter alleviated competition stress from S. canadensis on I. cylindrica. We conclude that winter glyphosate application can increase the selectivity and efficiency of chemical control of invasive S. canadensis, which may shift the competition balance towards native species and favour native vegetation recovery in sites invaded by S. canadensis. The principles of this approach can be applied to any scenario where invasive species and co-occurring species have distinct phenological niche separation.