Amajor step towards reliable reading of information coded in the sequence of long poly(phosphodiester)s was previously achieved by introducing an alkoxyamine spacer between information sub-segments.H owever,M S/MS decoding had to be performed manually to safely identify useful fragments of low abundance compared to side-products from the amide-based alkoxyamine used. Here,a lternative alkoxyamines were designed to prevent side-reactions and enable automated MS/MS sequencing.D ifferent styryl-TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure.T heir dissociation behavior was investigated by EPR and best results were obtained with spacers containing in-chain benzyl ring, with no side-reaction during synthesis or sequencing.A utomated decoding of these polymers was performed using the MS-DECODER software, which interprets fragmentation data recorded for each subsegment and realign them in their original order based on location tags.