Hybrid nanomaterials can have superior properties in comparison with individual components, sometimes greatly improving their optoelectronic activity. For this reason, modified carbon electrodes were obtained using a hybrid material composed of 5,10,15,20-tetra(4-tolyl)porphyrinato manganese (III) chloride (MnTTP) embedded in a silica matrix. The laser ablation deposition technique (PLD) has been used to immobilize the manganese porphyrin–silica hybrid on the surface of the carbon electrodes. The successful transfer of the manganese-porphyrin was evidenced by UV–Vis absorption spectroscopy. The PLD-deposited hybrid film was characterized using AFM and electrochemical methods (cyclic voltammetry and square wave voltammetry). The viability of this hybrid nanomaterial film as a redox mediator for the anodic oxidation and sensitive voltammetric determination of ascorbic acid in buffer solution (pH = 6.5) is described. The recorded anodic process is attributed to its oxidation to dehydroascorbic acid, with satisfactory catalytic current response and low non-Faradaic current.