Although the addition of acid halides across olefins is well-studied, limitations remain with a number of substrate classes that possess leaving groups, polyunsaturation, and acid-sensitive moieties, particularly polyenes prone to cyclization. The process is also challenging when conducted on a small scale, and moreover, methods for the addition of their deuterated counterparts typically require special techniques, especially when control of stoichiometry is required. Herein is described a readily synthesized and handled reagent class which can accomplish the controlled and selective Markovnikov addition of both HCl and HBr across several alkene classes under mild reaction conditions tolerant of diverse functionality. The process is particularly valuable on a laboratory scale, and direct comparisons to other methods are provided. As a result of in-depth mechanistic studies seeking to understand how these novel tools work and the active species behind their efficacy, the means to easily add DCl and DBr using a controlled amount of D2O was discovered along with the critical role of hydrolysis in leading to active hydrohalogenation species.