Autoxidation processes to achieve curing of alkyd resins in paints, inks, and coatings are ubiquitous in many applications. Cobalt soaps have been employed for these applications for many decades and most of the paint and ink alkyd resin formulations have been optimized to achieve optimal benefits of the cobalt soaps. However, cobalt soaps are under increased scrutiny because of likely reclassification as carcinogenic under REACH (Registration, Evaluation, Authorisation, and Restrictions of Chemicals) legislation in Europe. This is critical, since such coatings are available for regular human contact. Alternative manganese- and iron-based siccatives have been developed to address this need for over a decade. They often show very high curing activity depending on the organic ligands bound to the metal centers. Recently, new classes of catalysts and modes of application have been published or patented to create safe paints, whilst delivering performance benefits via their unique reaction mechanisms. Besides the use of well-defined, preformed catalysts, paint formulations have also been developed with mixtures of metal soaps and ligands that form active species in-situ. The change from Co-soaps to Mn- and Fe-based siccatives meant that important coating issues related to radical-based curing, such as skinning, had to be rethought. In this paper we will review the new catalyst technologies and their performance and modes of action, as well as new compounds developed to provide anti-skinning benefits.