Department of Chemistry, University of Allahabad, Allahabad-211 002, Uttar Pradesh, India E-mail : rajmanichemistry@gmail.com, mcc46@rediffmail.com Manuscript received online 16 January 2013, revised 11 February 2013, accepted 17 February 2013 The charge transfer complex (CTC) formed by FeIII with 5-sulphosalicylic acid 5-chlorosalicylic acid were studied using spectrophotometric method in mixed solvent system. Four solvent mixtures were taken having variation in amount of 1,4-dioxane as 5, 10, 15 and 20%. In acid range of pH 1–3, both the ligands formed 1 : 1 complex. A graphical method with computer software program was developed for determination of stability constant and molar absorptivity of 1 : 1 complex at pH 2.35 ± 0.05 and ionic strength 0.1 M, maintained by NaClO4 . This approach gave better value than obtained from graphical method neglecting certain terms to make a linear plot. It was observed that both the value of stability constant as well as molar absorptivity increases with increase in the percentage of 1,4-dioxane in the mixed solvent.