Foam products are one of the largest markets for polyurethane (PU) and are heavily used in many sectors. However, current PU formulations use highly toxic and environmentally unfriendly production processes. Meanwhile, the increasing environmental concerns and regulations are intensifying the research into green and non-toxic products. In this study, we synthesized flexible polyurethane foam (PUF) using different weight percentages (0.025%, 0.05% and 0.1%) of a non-toxic bismuth catalyst. The bismuth-catalyzed foams presented a well evolved cellular structure with an open cell morphology. The properties of the bismuth-catalyzed flexible PUF, such as the mechanical, morphological, kinetic and thermal behaviors, were optimized and compared with a conventional tin-catalyzed PUF. The bismuth-catalyst revealed a higher isocyanate conversion efficiency than the stannous octoate catalyst. When comparing samples with similar densities, the bismuth-catalyzed foams present better mechanical behavior than the tin-catalyzed sample with similar thermal stability. The high solubility of bismuth triflate in water, together with its high Lewis acidity, have been shown to benefit the production of PU foams.