Side-chain engineering and modifications of different polysaccharides led to a series of spontaneously assembled nanovehicles with a self-adjusting aptitude. Experimental studies supported by atomistic molecular dynamics simulations revealed that the prepared nanovehicles could encapsulate molecular cargoes of various polarities (from highly hydrophobic to ionic compounds) in aqueous and lipid environments and transport them through biological barriers. The prepared polymers demonstrated effective transdermal delivery of medicines, among them insulin, transportation of highly ionic plant nutrients via leaf cuticle and stimuli-responsive release of food protectants. The reported polysaccharide-based nanovehicles hold remarkable potential as effective biocompatible delivery systems in broad range applications in medicine, cosmetics, food and agriculture.