This paper reports the first experimental observation of ultrafast charge transfer in photo-excited MoS₂/WS₂ heterostructures using photoluminescence mapping and femtosecond pump-probe spectroscopy. The study demonstrates that hole transfer from the MoS₂ layer to the WS₂ layer occurs within 50 fs after optical excitation, a rate that is remarkable for van der Waals coupled 2D layers. The findings highlight the potential of MX₂ heterostructures for novel optoelectronic and photovoltaic applications due to their efficient electron-hole separation and strong light-matter interactions. The ultrafast charge transfer process is attributed to the type-II band alignment in the heterostructure, where the conduction band minimum resides in MoS₂ and the valence band maximum in WS₂, facilitating efficient charge separation. The study also discusses the challenges and implications of charge transfer in MX₂ heterostructures, emphasizing the importance of further theoretical and experimental investigations to understand the hybridization of electronic states and the dynamic evolution of photo-excited states.This paper reports the first experimental observation of ultrafast charge transfer in photo-excited MoS₂/WS₂ heterostructures using photoluminescence mapping and femtosecond pump-probe spectroscopy. The study demonstrates that hole transfer from the MoS₂ layer to the WS₂ layer occurs within 50 fs after optical excitation, a rate that is remarkable for van der Waals coupled 2D layers. The findings highlight the potential of MX₂ heterostructures for novel optoelectronic and photovoltaic applications due to their efficient electron-hole separation and strong light-matter interactions. The ultrafast charge transfer process is attributed to the type-II band alignment in the heterostructure, where the conduction band minimum resides in MoS₂ and the valence band maximum in WS₂, facilitating efficient charge separation. The study also discusses the challenges and implications of charge transfer in MX₂ heterostructures, emphasizing the importance of further theoretical and experimental investigations to understand the hybridization of electronic states and the dynamic evolution of photo-excited states.