Waste-to-energy conversion presents a pivotal strategy for mitigating the energy crisis and curbing environmental pollution. Pyrolysis is a widely embraced thermochemical approach for transforming waste into valuable energy resources. This study delves into the co-pyrolysis of terrestrial biomass (potato peel) and marine biomass (Sargassum angastifolium) to optimize the quantity and quality of the resultant bio-oil and biochar. Initially, thermogravimetric analysis was conducted at varying heating rates (5, 20, and 50 °C/min) to elucidate the thermal degradation behavior of individual samples. Subsequently, comprehensive analyses employing FTIR, XRD, XRF, BET, FE-SEM, and GC-MS were employed to assess the composition and morphology of pyrolysis products. Results demonstrated an augmented bio-oil yield in mixed samples, with the highest yield of 27.1 wt% attained in a composition comprising 75% potato peel and 25% Sargassum angastifolium. As confirmed by GC-MS analysis, mixed samples exhibited reduced acidity, particularly evident in the bio-oil produced from a 75% Sargassum angastifolium blend, which exhibited approximately half the original acidity. FTIR analysis revealed key functional groups on the biochar surface, including O-H, CO, and C-O moieties. XRD and XRF analyses indicated the presence of alkali and alkaline earth metals in the biochar, while BET analysis showed a surface area ranging from 0.64 to 1.60 m2/g. The favorable characteristics of the products highlight the efficacy and cost-effectiveness of co-pyrolyzing terrestrial and marine biomass for the generation of biofuels and value-added commodities.