B-Cyanodicarba-closo-dodecaboranes are a poorly explored class of compounds due to their complex synthetic availability. Now, we report a fast, atom-efficient, and high-yielding synthesis. We obtained the cyano derivatives by reacting B-iododicarba-closo-dodecaboranes with copper(I) cyanide under both palladium catalysis and microwave irradiation. We successfully applied this method to 9-iodo-o-, 9-iodo-m-, and 2-iodo-p-dicarba-closo-dodecaborane, obtaining the corresponding cyanides up to 89% isolated yield. The facile synthesis and evaluation of their spectroscopic properties reported herein will pave the way to exploring the chemistry and application of B-cyanodicarba-closo-dodecaborane clusters in more detail.