The assessment of residue, absorption, conduction, and degradation of agricultural organosilicon surfactants in the environment is hindered by the lack of information on active ingredients and corresponding quantitative standards for organosilicon spray adjuvants. The spray adjuvant ‘Jiexiaoli,’ a primary organosilicon spray agent in China, was identified as hydroxy (polyethylene) propyl‐heptamethyl trisiloxane (TSS‐H) with 3–15 ethoxy (EO) groups. Purification of TSS‐H was achieved through semi‐preparative separation using high‐performance liquid chromatography (HPLC), resulting in TSS‐H purity exceeding 96%. An accurate residual detection method for nine oligomers (4–12 EO) of TSS‐H in rice roots, stems, leaves, and culture solution samples was developed using HPLC tandem high‐resolution mass spectrometry (HPLC‐HRMS). Recoveries for nine oligomers of TSS‐H in the four matrices ranged from 80.22% to 104.01%. Foliar application experiments demonstrated that TSS‐H did not transfer from the upper to the lower parts of the rice plant. The half‐lives of each oligomer (4–12 EO) in leaves were less than 3.21 days. Root application experiments revealed a root concentration factor (RCF) ranging from 0.20 to 0.56, a biological enrichment factor (BCF) ranging from 0.36 to 0.68, a transpiration factor (TSCF) ranging from 0.069 to 0.086, and a transport factor (TF) ranging from 0.08 to 0.43. These results indicated that TSS‐H could be absorbed by rice roots and conducted to the above‐ground parts of rice plants. This study fills the data gap in the environmental risk and food safety assessment of agricultural silicone spray adjuvants. © 2024 Society of Chemical Industry.