International audienceHigh-capacity digital poly(phosphodiester)s were synthesized by stepwise automated phosphoramidite chemistry. Coding libraries containing either 4 or 8 phosphoramidite monomers of different mass were used to encode the polymers, thus enabling storage densities of 2 or 3 bits/monomer, respectively. In addition, a monomer containing a cleavable alkoxyamine and nucleotide mass tags enabling fragment identification were included in the chains to allow their decryption by electrospray pseudo-MS3 sequencing. As a proof of concept, black and white images with sizes ranging from 80 to 144 pixels were encoded in single polymer chains and decoded by mass spectrometry. Six different polymers were prepared in this work; three with...