Alkali vapours, such as rubidium, are being used extensively in several important fields of research such as slow and stored light nonlinear optics quantum computation, atomic clocks and magnetometers. Recently, there is a growing effort towards miniaturizing traditional centimetre-size vapour cells. Owing to the significant reduction in device dimensions, light–matter interactions are greatly enhanced, enabling new functionalities due to the low power threshold needed for nonlinear interactions. Here, taking advantage of the mature platform of silicon photonics, we construct an efficient and flexible platform for tailored light–vapour interactions on a chip. Specifically, we demonstrate light–matter interactions in an atomic cladding waveguide, consisting of a silicon nitride nano-waveguide core with a rubidium vapour cladding. We observe the efficient interaction of the electromagnetic guided mode with the rubidium cladding and show that due to the high confinement of the optical mode, the rubidium absorption saturates at powers in the nanowatt regime.