Vitrimers constitute a fascinating class of polymer materials that make the link between the historically opposed 3D networks (thermosets) and linear polymers (thermoplastics). Their chemical resistance, reshaping ability, and unique rheological behavior upon heating make them promising for future applications in industry. However, many vitrimers require the use of high catalyst loadings, which raises concerns for their durability and limits their potential applications. To cope with this issue, internal catalysis and neighboring group participation (NGP) can be used to enhance the reshaping ability of such materials. A few studies report the effect of activating groups on the exchange reactions in vitrimers. Nevertheless, knowledge on this topic remains scarce, although research on vitrimers would greatly benefit from NGP already known in organic chemistry. The present Perspective presents the different types of exchangeable bonds implemented in vitrimers and discusses chemical groups known to have or potentially capable of an enhancing effect on exchange reactions. This analysis is underpinned by a thorough mechanistic discussion of the various exchangeable bonds presented.