The delegation will be led by Defense Minister Rustem Umerov, writes Zelenskyj on Telegram.
"We are doing everything we can to protect our independence, our state and our people", writes the President.
Russia is also sending a delegation for a new round of direct talks, reports state-controlled Russian news agencies.
Russia said last week that it was ready to meet Ukrainian representatives in Istanbul, Turkey on Monday and present a new peace proposal.
Expectations are, however, low after President Vladimir Putin failed to show up at a high-level meeting with Ukraine's Volodymyr Zelenskyj in Istanbul in mid-May. Instead, representatives met at a much lower level and no major breakthroughs were made.
Russia launched its large-scale war of aggression against its neighboring country over three years ago. In recent months, attempts to achieve a ceasefire and peace talks have intensified, particularly with the pressure from US President Donald Trump. Russia has, however, signaled that it will not agree to an unconditional ceasefire.
