Korolevska became a member of All-Ukrainian Union "Fatherland" (a part of Bloc Yulia Tymoshenko) in autumn 2005 because "she is sure that the block of Yulia Tymoshenko is the future".[15] Korolevska decided to enter national politics: "I knew the most complex problems of the Donbas and sincerely wanted to solve them, but saw and understood that it is impossible to do so at the level of the regional council. It is in this spirit that I arrived in the Verkhovna Rada (Ukrainian parliament) in 2006. Disappointment came quickly enough: it seems that everyone here is well aware of the difficulties, but nobody makes an attempt [to] resolve them and to help the people."[18] During the 2006 and 2007 parliamentary elections, she was elected as a deputy to the Verkhovna Rada. During these tenures Korolevska served as the chairperson of the committee on the issues of industrial and regulatory policy and entrepreneurship in the Verkhovna Rada.[12][19][20][21][22]
On 23 December 2011, Korolevska was elected the leader of the Ukrainian Social Democratic Party (just like her former party, that party was also a member of the Yulia Tymoshenko Bloc).[2] Hence she did not change faction in the Verkhovna Rada.[2]
On 14 March 2012 Korolevska was expelled from her "Bloc Yulia Tymoshenko-Batkivschyna"-faction after refusing to vote for the inclusion of a proposal in the agenda of the Verkhovna Rada (according to the faction, Korolevska claimed her "voting card" was stolen and that she wanted to vote for the proposal[25]).[26]
The faction stated Korolevska was expelled "for breach of parliamentary ethics and cooperation with the Presidential Administration"; she had been reprimanded previously.[25][27] Two deputies of the "Yulia Tymoshenko Block-Batkivschyna" faction, who were like Korolevska members of the Ukrainian Social Democratic Party,[28] resigned from the faction in protest against Korolevska's expelling the same day.[29]
Korolevska was re-elected, placed 4th on the party list of Opposition Platform — For Life this time, in the 2019 Ukrainian parliamentary election.[46] Her husband Yuriy Solod was also re-elected in constituency No. 47 for the same party.[46] Ukrainian journalists discovered that Korolevska failed to disclose her ownership of real estate in Russia's Moscow Oblast for 16 years in a row; in addition, she has allegedly owned real estate and a plot of land in Russia since 2005.[47]
In February 2023 Korolevska and her husband Solod asked for the deprivation of their parliamentary mandates for "health and family circumstance."[10] On 24 February 2023 parliament withdrew their mandates.[10]
In December 2022, National Agency on Corruption Prevention revealed that Korolevska had financially enriched herself as a deputy of Rada by almost UAH 50 million and she had deliberately declared dishonest data about his income; her tax declaration in 2020 differed by UAH 3,8 million from the reliable ones.[50]
"Almost 20 years spent talking about European values and the principles of democracy has led us to the world of illusions and double standards."
Korolevska during the Yalta European Strategy conference 2011[52]
Korolevska political goal is "to create an efficient, transparent and stable economy"[53] with less Government involvement.[17] She claims to stand for political reforms to combat poverty and corruption.[53] Korolevska wants to involve the non-government sector more in decision-making.[52] She is against re-privatization.[54]
In February 2012 she accused the Azarov Government of being "amateurish" "and it doesn't seem to notice that the country is on the verge of default".[55]
Korolevska sees herself as a representative of the upcoming generation of political leaders of Ukraine.[52] In 2007 "Focus" magazine placed Korolevska 66th in a survey investigating the most influential women of Ukraine.[60] In 2009 she reached the 9th spot in that survey (six places higher than the Minister of Labor and Social Policy Lyudmyla Denisova);[61] "in 2009 she increased her presence in the coal market of Ukraine", according to Focus.[62]
In February 2008 Focus placed Korolevska at the 93rd place in their ranking of the richest Ukrainians.[17] Experts of the magazine assessed her assets to be worth US$ 243 million (in the food industry).[17] According to Korolevska she is no longer active in business and her husband controls her assets.[54]
According to media in Luhansk Korolevska was one of the most influential figures in that region.[17]
According to experts Korolevska spend about $1.25 million on a spring 2012 national billboards campaign aimed at raising her profile; her press service did not give any figures about expenditures on this ad campaign, stating it was a "commercial secret".[63]