Over the past decade, research fields of MOFs and SERS rapidly progressed and only recently they merged into new analytical platforms that are particularly well suited for the analysis of VOCs. Throughout this review, the intricate interplay of both MOFs and metallic nanostructures is discussed together with important design rules enabling maximizing performance of MOF-based SERS substrates. For example, the way in which MOFs grow on a metallic surface is dictated not only by the nature of the MOF itself, but also by the metallic nanostructure that impacts on the internal structure of the MOF phase, subsequently affecting the permeation of analytes towards the SERS-active surface. Therefore, understanding of this complex interplay is essential for successful design, characterizing, and optimizing the performance of MOF-based SERS substrates in terms of amplification of optical signal and ability to preconcentrate target analyte species within the plasmonic hotspots.