The wettability of graphene remains controversial owing to its high sensitivity to the surroundings, which is reflected by the wide range of reported water contact angle (WCA). Specifically, the surface contamination and underlying substrate would strongly alter the intrinsic wettability of graphene. Here, the intrinsic wettability of graphene is investigated by measuring WCA on suspended, superclean graphene membrane using environmental scanning electron microscope. An extremely low WCA with an average value ≈30° is observed, confirming the hydrophilic nature of pristine graphene. This high hydrophilicity originates from the charge transfer between graphene and water molecules through H–π interaction. The work provides a deep understanding of the water–graphene interaction and opens up a new way for measuring the surface properties of 2D materials. With the assistance of environmental scanning electron microscope, the high hydrophilic nature of pristine graphene with an extremely low water contact angle of ≈30° is confirmed, using the suspended, superclean graphene membrane to exclude the interference by substrates and contamination. This high hydrophilicity is revealed to originate from the charge transfer between graphene and water molecules through H–π interaction.