Carbon-carbon multiple bonds (alkenes, alkynes and allenes) are versatile functionalities for transition metal-catalysed carbon-carbon and carbon-heteroatom coupling reactions. Despite their increasing synthetic utility with recent improvements in regio- and stereoselectivity, substantial issues remain regarding selectivity among the types of C-C multiple bonds due to their relative reactivities towards a catalyst when they coexist in a reaction. Here, we present a Pd-catalysed hydroamination¹ that is highly selective for either the allene or alkyne of an aminoallenyne. We determined the relative reactivity of alkene, alkyne, allene, and amine towards the Pd catalyst using time-dependent fluorescence quenching to explain the selectivity and the reaction mechanism. Additionally, we developed a tandem reaction combining the selective hydroamination of either alkyne or allene with C-C and C-O couplings. References 1 (a) Huang, L.; Arndt, M.; Gooβen, K.; Heydt, H.; Gooβen, L. J. Chem. Rev. 2015, 115, 2596-2697. (b) Muller T. E., Hultzsch K. C., Yus M., Foubelo F. & Tada M. Chem. Rev. 108, 3795-3892 (2008). (c) Reznichenko A. L. & Hultzsch K. C. Organic Reactions 88, 1-554 (2004).