Pembélé joined the Paris Saint-Germain Academy at the age of 13 in 2015, having spent the previous seven years of his youth career at US Persan 03.

[5] On 28 November 2020, Pembélé made his professional debut in a 2–2 Ligue 1 draw against Bordeaux, starting as a right center-back in a pairing with Presnel Kimpembe.

He made good use of his speed and vision in defense, recovering the ball on several occasions,[8] and helped his team move forward in attack with several successful vertical passes.

[11] He made his UEFA Champions League debut five days later, coming on as a substitute for Alessandro Florenzi in a 5–1 win against İstanbul Başakşehir.

After nine months on the sidelines, he made his return to play in a friendly game on 19 January 2023, coming on as a substitute in a 5–4 win over the hybrid Riyadh Season Team.

According to Culture PSG, Pembélé is a quick player equipped with good technique, and he constantly brings an offensive threat on his side of the pitch.

[30] Pembélé is adept at stealing the ball of attackers with his pace and tenacity, using his technique to turn while hugging the touchline, and accelerating past the opponent he was marking moments earlier.