Abstract: An ion pair HPLC method for the separation and determination of various water-soluble derivatives of andrographolides, e. g. andrographolide sodium bisulfite additive, andrographolide sodium sulfonate, andrographolide triacetyl sodium sulfonate and their preparations, is reported. The counter-ion used in this method is 0.08% hexadecyl trim-ethyl ammonium bromide (Cetrimid). The most suitable pH value is 3～4. All of the derivatives can be completely separated from each other and determined individually with silica gel column normal phase chromatography by nv at λ 220 nm while using isopropanol:n-pentanohwater (65:27:7)as mobile phase and picric acid as internal stand-ard. This method exhibited very high sensitivity and selectivity. The minimum detect-able quantity is 1×10^-5 gm with high accuracy.