The simultaneous synthesis of gold nanoparticles (AuNPs) and graphene by laser ablation was demonstrated. The in-situ synthesis was performed by laser ablation of a polymer substrate covered with a gold precursor dispersion. The gold precursor was prepared in a copolymer solution of pyrrole (Py) and chitosan (Chi) to improve the nucleation of gold embedded on the laser-induced graphene electrode (LIGE). The morphology of AuNPs-pPy-Chi/LIGE was studied by scanning electron microscopy and characterized electrochemically by cyclic voltammetry. A comprehensive investigation of the electrochemical and physical features of the AuNPs-pPy-Chi/LIGE was carried out. The parameters of differential pulse voltammetry were adjusted to enhance the response to ascorbic acid (AA). The AuNPs-pPy-Chi/LIGE produced two linear ranges: from 0.25 to 5.00 and 5.00–25.00 mmol L−1. The limit of detection was 0.22 mmol L−1. Hundreds of electrodes were tested to demonstrate the excellent reproducibility of the AuNPs-pPy-Chi/LIGE fabrication. Overall, the proposed electrode allows the successful detection of AA in orange juice products with acceptable accuracy (recoveries = 97 ± 2 to 109.1 ± 0.7). The preparation strategy of the proposed AuNPs-pPy-Chi/LIGE could be adapted to detect other compounds or biomarkers.