Photopolymerization of acrylates under mild conditions is promising not only for academic research but also for industrial applications. However, it still remains a huge challenge to develop effective photoinitiators or photoinitiating systems for the free radical polymerization of acrylates under visible light-emitting diode (LED) irradiation. In this work, twelve novel ketone derivatives containing either tertiary amines or anthracenes as peripheral substituting groups (noted as Ami-1–Ami-6 and Anth-1–Anth-6) were elaborately synthesized and proposed for the polymerization of di(trimethylolpropane) tetraacrylate (TA), a tetrafunctional polyether acrylate, under both thin and thick film conditions under LED@405 nm irradiation. Remarkably, eight of the selected ketones (Ami-2, Ami-6, Anth-1–Anth-6) had never been synthesized before. In combination with an amine and/or an iodonium salt (Iod), these ketones could form distinct photoinitiating systems, among which the Ami-2/amine/Iod system could lead to the highest final conversion of acrylates under the thick film (∼1.4 mm) conditions while the Ami-6/amine/Iod system could induce the highest final conversion of acrylates under the thin film (∼25 μm) conditions. The photosensitivity of Ami-2 and Ami-6 was systematically investigated by steady state photolysis and fluorescence quenching experiments. Finally, the photocuring 3D printing technique was applied to TA, and both Ami-2- and Ami-6-based photoinitiating systems could be used to fabricate macroscopic 3D patterns with excellent spatial resolution.