Photoelectrochemical (PEC) systems are promising approaches for sustainable fuel processing. PEC devices, like conventional photovoltaic-electrolyzer (PV-EC) systems, utilize solar energy for splitting water into hydrogen and oxygen. Contrary to PV-EC systems, PEC devices integrate the photoabsorber, the ionic membrane, and the catalysts into a single reactor. This integration of elements potentially makes PEC systems simpler in design, increases efficiency, offers a cost advantage, and allows for implementation with higher flexibility in use. We present a detailed techno-economic evaluation of PEC systems with three different device designs. We combine a system-level techno-economic analysis based on physical performance models (including degradation) with stochastic methods for uncertainty assessments, also considering the use of PV and EC learning curves for future cost scenarios. For hydrogen, we assess different PEC device design options (utilizing liquid or water vapor as reactant) and compare them to conventional PV-EC systems (anion or cation exchange). We show that in the current scenario, PEC systems (with a levelized cost of hydrogen of 6.32 $/kgH2) located in southern Spain are not yet competitive, operating at 64% higher costs than the PV-driven anion exchange EC systems. Our analysis indicates that PEC plants’ material and size are the most significant factors affecting hydrogen costs. PEC designs operating with water vapor are the most economical designs, with the potential to cost about 10% less than PV-EC systems and to reach a 2 $/kgH2 target by 2040. If a sunlight concentrator is incorporated, the PEC-produced hydrogen cost is significantly lower (3.59 $/kgH2 in the current scenario). Versions of the concentrated PEC system that incorporate reversible operation and CO2 reduction indicate a levelized cost of storage of 0.2803 $/kWh for the former and a levelized cost of CO of 0.546 $/kgCO for the latter. These findings demonstrate the competitiveness and viability of (concentrated) PEC systems and their versatile use cases. Our study shows the potential of PEC devices and systems for hydrogen production (current and future potential), storage applications, and CO production, thereby highlighting the importance of sustainable and cost-effective design considerations for future advancements in technology development in this field.