A series of boron based Lewis acids have been reported to date, but among them, tris(pentafluorophenyl)borane (BCF) has gained the most significant attention in the synthetic chemistry community. The viability of BCF as a potential Lewis acid catalyst has been vastly explored in organic and materials chemistry due to its thermal stability and commercial availability. Most explorations of BCF chemistry in organic synthesis has occurred in the last two decades and many new catalytic reactivities are currently under investigation. This review mainly focuses on recent reports from 2018 onwards and provides a concise knowledge to the readers about the role of BCF in metal-free catalysis. The review has mainly been categorized by different types of organic transformation mediated through BCF catalysis for the C-C and C-heteroatom bond formation.