Two-dimensional (2D) ultrathin bismuth tungstate (Bi2WO6) nanosheets (BWO-NS) with a thickness of approximately 4.0 nm were synthesized by a one-step hydrothermal method, and decorated with platinum (Pt) nanoparticles (NPs) via an impregnation/borohydride-reduction approach. The as-prepared ultrathin Pt-BWO-NS exhibited superior catalytic activity for removing gaseous formaldehyde (HCHO) at ambient temperature, in comparison with bulk counterpart with Bi2WO6 sheet thickness of tens of nanometers. The ultrathin structure endowed the Pt-BWO-NS sample with larger specific surface area, which can provide abundant surface active sites for HCHO adsorption and facilitate the homogeneous dispersion of Pt NPs. X-ray photoelectron spectroscopy and hydrogen temperature-programmed reduction analyses revealed the interaction between the Bi2WO6 support and Pt species, which is crucial for activating surface oxygen atoms to participate in the catalytic HCHO oxidation process. By conducting in situ diffuse reflectance infrared Fourier transform spectroscopy under different atmospheres, i.e., gaseous HCHO in nitrogen or oxygen (O2), the reaction mechanism and the role of O2 were elucidated, with dioxymethylene, formate and linearly adsorbed carbon monoxide identified as the main reaction intermediates. This study may provide new enlightenment on fabricating novel 2D nanomaterials for efficient indoor air purification and potentially other environmental applications.