There have been significant advances in adhesive dentistry in recent decades, with efforts being made to improve the mechanical and bonding properties of resin-based dental adhesive materials. Various attempts have been made to achieve versatility, introducing functional monomers and silanes into the materials’ composition to enable the chemical reaction with tooth structure and restorative materials and a multimode use. The novel adhesive materials also tend to be simpler in terms of clinical use, requiring reduced number of steps, making them less technique sensitive. However, these materials must also be reliable and have a long-lasting bond with different substrates. In order to fulfill these arduous tasks, different chemical constituents and different techniques are continuously being developed and introduced into dental adhesive materials. This critical review aims to discuss the concepts behind novel monomers, bioactive molecules, and alternative techniques recently implemented in adhesive dentistry. Incorporating monomers that are more resistant to hydrolytic degradation and functional monomers that enhance the micromechanical retention and improve chemical interactions between adhesive resin materials and various substrates improved the performance of adhesive materials. The current trend is to blend bioactive molecules into adhesive materials to enhance the mechanical properties and prevent endogenous enzymatic degradation of the dental substrate, thus ensuring the longevity of resin–dentin bonds. Moreover, alternative etching materials and techniques have been developed to address the drawbacks of phosphoric acid dentin etching. Altogether, we are witnessing a dynamic era in adhesive dentistry, with advancements aiming to bring us closer to simple and reliable bonding. However, simplification and novelty should not be achieved at the expense of material properties.