At room temperature, methylbenzene-acetone-formic acid (9∶9∶2, V/V), methylbenzene-ethyl formate- methanol-formic acid (5.0∶10.0∶1.0∶0.5, V/V), methylbenzene-chloroform-acetone-formic acid (8.0∶5.0∶15.0∶0.3, V/V), chloroform-acetone-methanol-water (12.5∶7.5∶1.8∶0.6, V/V) and chloroform-acetone-formic acid-water (12.5∶7.5∶1.8∶0.6, V/V) on silica gel marked as solventⅠ, Ⅱ, Ⅲ, Ⅳ and Ⅴrespectively were applied as developing solvent respectively in high performance thin-layer chromatography (HPTLC) for isolating catechins in the tea. Among them, solvent Ⅴ was found to be the best for separation of catechins, this solvent was then modified mainly regarding the volume ratios of formic acid. The results showed the modified solvent Ⅴ, namely, chloroform- acetone- formic acid (12.5∶7.5∶2.2, V/V) was the optimum for separation of the four main catechins (EGCg, EGC, ECg, EC) in the tea. The applicability of the optimized developing solvent was further confirmed by separation of catechins in the extracts of the green and the white tea.