Red LED light (R LED) is an efficient tool to improve seed germination and plant growth under controlled environments since it is more readily absorbed by photoreceptors’ phytochromes compared to other wavelengths of the spectrum. In this work, the effect of R LED on the radicle emergence and growth (Phase III of germination) of pepper seeds was evaluated. Thus, the impact of R LED on water transport through different intrinsic membrane proteins, via aquaporin (AQP) isoforms, was determined. In addition, the remobilization of distinct metabolites such as amino acids, sugars, organic acids, and hormones was analysed. R LED induced a higher germination speed index, regulated by an increased water uptake. PIP2;3 and PIP2;5 aquaporin isoforms were highly expressed and could contribute to a faster and more effective hydration of embryo tissues, leading to a reduction of the germination time. By contrast, TIP1;7, TIP1;8, TIP3;1 and TIP3;2 gene expressions were reduced in R LED-treated seeds, pointing to a lower need for protein remobilization. NIP4;5 and XIP1;1 were also involved in radicle growth but their role needs to be elucidated. In addition, R LED induced changes in amino acids and organic acids as well as sugars. Therefore, an advanced metabolome oriented to a higher energetic metabolism was observed, conditioning better seed germination performance together with a rapid water flux.