<p>Imparting one-dimensional (1D) ultrafine organic nanowires with tailored ligands and atomically-dispersed central noble metal to craft high-performance hybrid single atom electrocatalysts offers a prospective yet challenging approach for the advancement in hydrogen evolution reactions (HER). Herein, we report the evaporation-induced self-assembly of sequence-defined amphiphilic alternating azopeptoids (AAAPs) to generate photo-responsive and micron-scale ultrafine peptoid nanowires (UFPNWs) with a diameter of ~1.8 nm via pendants’ hydrophobic conjugate stacking mechanism, exemplifying the finest biomimetic polymers-based nanowires to date. A series of 1D UFPNWs-based single-atom catalysts (SACs) were meticulously fabricated using the chelation interaction between Pt ions and nitrogenous ligands. The photo-controllable electrocatalytic performance was evaluated toward acidic HER, which was highly dependent on the presence of Pt elements, the structural characteristic of supports, and the peripheral coordination microenvironment of the center Pt atoms. Notably, the Pt-based hybrid SACs using terpyridine-modified UFPNWs as support presented favorable electrocatalytic capacity with an overpotential of ~20 mV at a current density of 10 mA cm⁻², and a mass activity of 89.6 times greater than commercial Pt/C catalyst. Our work paves an appealing avenue for the construction of stimuli-responsive 1D organic nanowire-based hybrid catalysts with controllable electrocatalytic HER performance.</p>