The tea plant accumulates elevated levels of fluoride (F) from environmental sources. Drinking tea containing high F levels poses a potential threat to human health. Selenium (Se) was applied by foliar spray to investigate its effects on F accumulation and physiology in tea plant. Foliar application of different forms of Se, i.e., Na2SeO3, Kappa-selenocarrageenan, Selenomethionine and Nanoselenium, reduced F content in tea leaves by 10.17 %−44.28 %, 16.12 %−35.41 %, 22.19 %−45.99 % and 22.24 %−43.82 %, respectively. Foliar spraying Se could increase F accumulation in pectin through increasing pectin content and pectin demethylesterification to bind more F in the cell wall, which decreased the proportion of water-soluble fluoride in tea leaves. Application of Se significantly decreased the contents of chromium (39.6 %−72.0 %), cadmium (48.3 %−84.4 %), lead (2.2 %−44.4 %) and copper (14.1 %−44.6 %) in tea leaves. Foliar spraying various forms of Se dramatically increased the Se content and was efficiently transformed into organic Se accounting for more than 80 % in tea leaves. All Se compounds increased peroxidase activity by 3.3 %−35.5 % and catalase activity by 2.6 %−99.4 %, reduced malondialdehyde content by 5.6 %−37.1 %, and increased the contents of chlorophyll by 0.65 %−31.8 %, carotenoids by 0.24 %−27.1 %, total catechins by 1.6 %−21.0 %, EGCG by 4.4 %−17.6 % and caffeine by 9.1 %−28.6 %. These results indicated that Se application could be served as a potential efficient and safe strategy diminishing the concentration of F in tea leaves.