Metal-organic frameworks (MOFs) are porous hybrid materials composed of metal ions and organic linkers, characterized by their crystallinity and by the highest known surface areas. MOFs structures present accessible cages, tunnels and modifiable pores, together with adequate mechanical and thermal stability. Their outstanding properties have led to their recognition as revolutionary materials in recent years. Analytical chemistry has also benefited from the potential of MOF applications. MOFs succeed as sorbent materials in extraction and microextraction procedures, as sensors, and as stationary or pseudo-stationary phases in chromatographic systems. To date, around 100 different MOFs form part of those analytical applications. This review intends to give an overview on the use of MOFs in analytical chemistry in recent years (2017–2019) within the framework of green analytical chemistry requirements, with a particular emphasis on possible toxicity issues of neat MOFs and trends to ensure green approaches in their preparation.