A simple and sensitive spectrophotometric method is developed for the determination of titanium in and vanadium in aqueous medium. The metal ions form a red coloured complex with 2’4-Dihydroxyacetophenone isonicotinoylhydrazone(RPINH) in the pH range 1-7. The complex shows absorption maximum at λmax 490nm and 400nm respectively. The molar absorptivity and sandell’s sensitivity of the method are 1.0 x 104 Lmol-1 cm-1 and 0.0048 μgcm-2 and 8.9 x 103 Lmol-1 cm-1 and 0.0056 μg cm-2 respectively. Beer’s law is obeyed in the range of 0.47- 3.35 μg ml-1 and 0.255 – 3.056 μg ml-1 respectively. A method for the determination of titanium and vanadium by first order derivative spectrophotometry is also proposed. The methods have been employed successfully for the determination of titanium and vanadium in several water, alloy and steel samples.