Two established techniques have been coupled to allow surfaces to be precision engineered. Electrospray ionization to bring large, complex, intact molecular ions into the gas phase has been interfaced with a radio frequency ͑rf͒ plasma reactor to treat surfaces making them receptive to the deposition of active biomolecules. The new instrument has been designed and used successfully to deposit a number of high molecular weight molecules including the polysaccharide, sodium hyaluronan ͑HA͒, that has an important role in a number of physiological functions. Substrate material is treated using a rf glow discharge plasma chamber, to clean and activate the surface in a controlled manner, then exposed to a beam of multiply charged ions in the gas phase that have been generated using electrospray techniques. The ions are deposited gently onto the substrate and become covalently bound. The molecular integrity and stability of HA surfaces prepared in this way was established using x-ray photoelectron spectroscopy, changes in the observed contact angle, time-of-flight secondary ion mass spectrometry, scanning electron microscopy, and a biological assay-platelet adhesion to the surface.