Momilactones A (MA) and B (MB) are known as phytoalexins which principally play a role in the rice defense system against pathogens. This is the first study revealing that MA and MB contribute to rice tolerance to environmental stresses, including ultraviolet (UV) radiation and chilling conditions. The proofs were achieved by scrutinizing the responses of rice under stresses through the expression of relevant biosynthetic genes to momilactones (MRBG) and phenolics (PRBG) and their accumulation. Accordingly, the expression tendency of PRBG was in line with that of MRBGs, which increased under UV irradiation but decreased under chilling conditions. In UV-exposed rice, the proliferation of MA and MB strongly correlated to that of salicylic and chlorogenic acids, esculetin, rutin, and fisetin. In terms of increasing chilling duration, the biosynthetic propensity of MB was consistent with that of benzoic, cinnamic, ρ-coumaric, salicylic, and syringic acids, quercetin, and tricin while the syntheses of MA and other compounds were reduced. The concomitant biosyntheses of momilactones with these acknowledged stress-resistant phenolics imply that momilactones might play a role as signaling molecules in the response mechanism of rice to UV and chilling stresses. Further comprehensive studies should be conducted to validate this paradigmatic finding.