Upconversion nanoparticle (UCNP)-driven polymerization attracts great attention due to the ability of near-infrared light to penetrate deeper into biological media and synthetic materials than ultraviolet or visible light. Despite significant progress, the limitation of near-infrared light-triggered polymerization is associated with a key element of the photocurable composition, a UCNP/photoinitiator complex or a nanoinitiator. To determine the impact of resonance energy transfer from UCNPs to photoinitiator (PI) and its effect on polymerization, we developed two different photocurable compositions consisting of the polyethylene glycol diacrylate (PEG-DA), ultraviolet- and blue-emitting NaYF4: Yb3+, Tm3+ UCNPs with hydrophobic surface combined with water-soluble or insoluble PI. We found that transfer energy in these nanoinitiators proceeds differently: in UCNP/water-soluble PI (lithium phenyl-2,4,6-trimethylbenzoylphosphinate or LAP), it occurs through the photon-mediated transfer while in UCNP/water-insoluble PI (2-benzyl-2-(dimethylamino)-4′-morpholinobutyrophenone or Irgacure 369), it takes place via the non-radiative resonant energy transfer. The impact of these processes in homolytic decomposition of initiator is extremely important in terms of the precisely controlled fabrication of polymer structures. PEG-DA facilitates the affinity between hydrophilic and hydrophobic components of the photocurable composition, which provides UCNP-driven cross-linking of biopolymers such as methacrylated hyaluronic acid and gelatin. 3D structures were prototyped to demonstrate the one-step rapid procedure of nanoinitiator preparation and emphasize the control of the energy transfer in UCNP/PI complexes for further development of UCNP-driven polymerization.