Vasylenko is a member of the Ukrainian permanent delegation to the Parliamentary Assembly of the Council of Europe and president of the Inter-Parliamentary Union's Bureau of Women Parliamentarians.

[2] After visiting a hospital during the war in Donbas in June 2014, Vasylenko learned that wounded soldiers were unaware of their rights to compensation.

In January 2015, she founded Legal Hundred [uk], a human rights non-governmental organization that provides assistance to servicemen and veterans.

[10] Vasylenko is a member of the Ukrainian parliamentary delegation to the Inter-Parliamentary Union[11] where she serves as president of its Bureau of Women Parliamentarians.

[13] On 12 December 2019, Vasylenko joined Humane country [uk], an inter-factional association to promote humanistic values and prevent cruelty to animals.