The current study demonstrated the capability of using maize silk as a green, simple, clean, safe, and cost-effective platform for the biosynthesis of cerium oxide (CeO2NPs). Several spectroscopic and microscopic analyses were employed to characterize the resulted biogenic nanoceria. When the concentration of the CeO2NPs was elevated from 25 to 100 ug mL−1, the CeO2NPs exhibited strong scavenging potential ranging from 60.21 to 75.11% and 56 to 77% for 1,1-diphenyl-2- picrylhydrazyl (DPPH•) and 2-2′-azino-bis(3-ethyl benzothiazoline-6-sulphonic acid) (ABTS) tests, respectively. The quantitative determination of ferulic, sinapic, and p-coumaric acids was carried out using an eco-friendly, cost-effective, and optimized ultrasensitive nanoceria enhanced sequential injection-chemiluminescence (SIA-CL) system. The highest amount was presented by the ferulic acid (1636 ± 2.61 ug/gdw), followed by p-coumaric acid (206 ± 1.12 ug/gdw) and sinapic acid (123 ± 2.15 ug/gdw). The intrinsic capabilities of the biogenic CeO2NPs in enhancing the developed system reveal its potential role in detecting phenolic compounds with great sensitivity.