Ligue 1 giants, PSG will compete in Europe's premier club competition for the first time since 2004/05 when they welcome Kyiv to Parc des Princes for their Group A encounter.
Carlo Ancelotti's men have made a solid if unspectacular start to their league campaign, drawing three games and winning their past two.
Star striker Zlatan Ibrahimovic has proven unstoppable since arriving in France, netting five league goals.
The Swedish international will need goalscoring support from the likes of Javier Pastore and Ezequiel Lavezzi if PSG are to progress in the Champions League.
In further good news for PSG, defender Thiago Silva, who joined with Ibrahimovic from AC Milan, is set to make his debut.
The Brazilian has been recovering from a thigh injury suffered at the London Olympics, delaying his first appearance for his new club.
Kyiv have made a strong start in the Ukrainian Premier League, losing just two of their opening nine games.
Nigerian Ideye Brown has provided a strong option up front with eight goals, while former Tottenham midfielder Niko Kranjcar has also settled well.
The Croatian international, whose side knocked out Borussia Moenchengladbach in the Champions League playoff round, has netted four league goals.
Elsewhere in Group A, Liga Sagres champions Porto visit Stadion Maksimir to take on Dinamo Zagreb.
Without striker Hulk, who moved to Russian side Zenit St Petersburg, Porto will rely on Lucho Gonzalez and James Rodriguez for their goals.
Dinamo Zagreb, meanwhile, are unbeaten this season with Brazilian Sammir leading the way to see them sitting top of the league.
It is a Zagreb side looking to atone for their miserable showing in the Champions League last season, when they lost all six games and conceded 22 goals in the group stages.
Included was a 7-1 thrashing at the hands of Lyon, a result which led to allegations of match-fixing.