The development of polymers photopolymerized from renewable resources are extensively growing as fulfills green chemistry and green engineering principles. With the rapid growth of consumerism, research on innovative starting materials for the preparation of polymers may help to reduce the negative impact of petroleum-based plastic materials on the global ecosystem and on animal and human health. Therefore, bio-based crosslinked polymers have been synthesized from functionalized soybean oil and squalene by thiol–ene ultra-violet (UV) curing. First, thiol–ene UV curing of squalene was performed to introduce thiol functional groups. Then, hexathiolated squalene was used as a crosslinker in click UV curing of acrylated epoxidized soybean oil. Two photoinitiators, 2-hydroxy-2-methylpropiophenone and ethylphenyl (2,4,6-trimethylbenzoyl) phosphinate, were tested in different quantities. Rheological properties of the resins were monitored by real-time photorheometry. The characterization of obtained polymers was performed by differential scanning calorimetry, thermogravimetry, and Shore A hardness measurements. Polymers possessed higher storage modulus, thermal characteristics, Shore A hardness, and lower swelling value when ethylphenyl (2,4,6-trimethylbenzoyl) phosphinate was used as photoinitiator.