In 2004 Guillaume obtained a Master in Chemistry from the Catholic University of Louvain (Belgium). He did his master thesis under the supervision of Prof István E. Markó on the development of platinum-based catalysts for the hydrosilylation of alkynes. He completed his PhD in 2009, in the same laboratory, working on the synthesis of angular triquinanes. He then took a post-doctoral position in the laboratory of Prof Jean-François Gohy and Charles-André Fustin (UCL, Belgium) to work on the assembly of mechanically-linked block copolymers. In 2011, he joined the group of Prof David A. Leigh, then in Edinburgh, to work on the development of molecular machines.
In 2015 he was awarded a Royal Society University Research Fellowship held at the University of Manchester to investigate the use of mechanical force in synthesis.