The development and application of new organoboron reagents as Lewis acids in synthesis and metal-free catalysis have dramatically expanded over the past 20 years. In this context, we will show the recent uses of the simple and relatively weak Lewis acid BPh3—discovered 100 years ago—as a metal-free catalyst for various organic transformations. The first part will highlight catalytic applications in polymer synthesis such as the copolymerization of epoxides with CO2, isocyanate, and organic anhydrides to various polycarbonate copolymers and controlled diblock copolymers as well as alternating polyurethanes. This is followed by a discussion of BPh3 as a Lewis acid component in the frustrated Lewis pair (FLP) mediated cleavage of hydrogen and hydrogenation catalysis. In addition, BPh3-catalyzed reductive N-methylations and C-methylations with CO2 and silane to value-added organic products will be covered as well along with BPh3-catalyzed cycloadditions and insertion reactions. Collectively, this mini-review showcases the underexplored potential of commercially available BPh3 in metal-free catalysis.