According to the document released today on the presidential website, a total of 2 507 individuals and 1 374 legal entities are blacklisted.
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The decision to sanction businessmen, military and government officials, as well as their families, came from the country's National Security and Defense Council (NSDC).
The sanctions are valid for five to ten years. Persons subject to them will see all their assets in Ukraine blocked. They will also be restricted from any business operations, transit through the country and flights to and from Ukraine.
The action also implies the suspension of all economic and financial obligations, as well as licenses and permits.
Russian telecommunications giant Rostelecom, Alfa-Bank, mining company and diamond manufacturer Alrosa, energy company RusHydro and the Russian Direct Investment Fund are among the legal entities blacklisted.
Earlier this month, Zelensky signed another decree ruling that any negotiations with Russian President Vladimir Putin were "impossible."
Large-scale sanctions against Russia, not only by Ukraine but also by several Western countries, have been commonplace since Russia's special military operation was launched in Ukraine last February.
Moscow has tirelessly accused Kiev of obstructing any possible means to resolve the ongoing conflict peacefully.