The use of light as a catalytic prompt for the synthesis of industrial relevant compounds is widely explored in the past years, with a special consideration over the hydrogen evolution reaction (HER). However, semiconductors for heterogeneous photocatalysis suffer from fast charge recombination and, consequently, low solar-to-hydrogen efficiency. These drawbacks can be mitigated by coupling photocatalysts with an external circuit that can physically separate the photogenerated charge carriers (electrons and holes). For this reason, photoelectrochemical (PEC) production of hydrogen is under the spotlight as promising green and sustainable technique and widely investigated in numerous publications. However, considering that a significant fraction of the hydrogen produced is used for reduction processes, the development of PEC devices for direct in situ hydrogenation can address the challenges associated with hydrogen storage and distribution. This Perspective aims at highlighting the fundamental aspects of HER from PEC systems, and how these can be harnessed toward the implementation of suitable settings for the hydrogenation of organic compounds of industrial value.