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A major 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. However, MS/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, alternative alkoxyamines were designed to prevent side‐reactions and enable automated MS/MS sequencing. Different styryl‐TEMPO spacers were prepared to increase radical delocalization and stiffness of the structure. Their 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. Automated decoding of these polymers was performed using the MS‐DECODER software, which interprets fragmentation data recorded for each sub‐segment and re‐align them in their original order based on location tags. [ABSTRACT FROM AUTHOR]