Photopolymerization
is an effective method to covalently cross-link
polymer chains that can be shaped into several biomedical products
and devices. Additionally, polymerization reaction may induce a fluid–solid
phase transformation under physiological conditions and is ideal for in vivo cross-linking of injectable polymers. The photoinitiator
is a key ingredient able to absorb the energy at a specific light
wavelength and create radicals that convert the liquid monomer solution
into polymers. The combination of photopolymerizable polymers, containing
appropriate photoinitiators, and effective curing based on dedicated
light sources offers the possibility to implement photopolymerization
technology in 3D bioprinting systems. Hence, cell-laden structures
with high cell viability and proliferation, high accuracy in production,
and good control of scaffold geometry can be biofabricated. In this
review, we provide an overview of photopolymerization technology,
focusing our efforts on natural polymers, the chemistry involved,
and their combination with appropriate photoinitiators to be used
within 3D bioprinting and manufacturing of biomedical devices. The
reviewed articles showed the impact of different factors that influence
the success of the photopolymerization process and the final properties
of the cross-linked materials.