A description is given of a process for the separation of at least one constituent from a mixture containing at least two polyglycerols having consecutive degrees of polymerization from 2 to 10, in which said mixture is passed into at least one column lined with an adsorbent particular phase through which flows a liquid eluent, said phase consisting of a cationic organic resin such as a styrene-divinyl benzene copolymer or an anionic resin, or a mineral phase chosen from among silicas, aluminas and zeolites in normal form or modified by grafting, said liquid eluent consisting of an aqueous phase to which is optionally added a strong acid. The process described can be performed continuously or batchwise and in simulated counter-current (SCC) or simulated cocurrent manner.