The results of floristic research in the territory of Kyiv City and its environs (in the adjacent territories of Kyiv Region) are presented. According to the results, five new taxa for the flora of Ukraine are reported: Cardamine occulta, Equisetum × moorei, Lolium × holmbergii, Limonium sinuatum, Lonicera maackii. Chrozophora tinctoria is a new species for the flora of the mainland part of Ukraine. Also, 16 new taxa were identified for the regional floras of the Ukrainian Polissya, Forest-Steppe, and Middle Dnipro regions. In addition, new locations of 69 rare aboriginal and expansive alien taxa are reported. In total, among the studied taxa 38 are native and 53 are alien. Among the studied alien plants, several are potentially invasive ones, and some of them have already demonstrated their invasive nature, in particular: Cornus sanguinea subsp. australis, Erigeron strigosus, Phragmites altissimus, and Vitis riparia. The results of our study confirm that the flora of Kyiv City and its environs is one of the richest floras in the plain part of Ukraine, and currently it is rapidly changing.