In the present research work, a novel method for spectrophotometric estimation of piroxicam tablets using melted niacinamide as solvent was developed. The main objective of the research is to show that solids also possess solubilizing power. The current study deals with a novel spectrophotometric analytical technique for quantitative estimation of piroxicam in tablets using melted niacinamide as solvent. According to the theory proposed by Maheshwari, each & every substance possesses solubilising power; the substance may be a gas, solid or liquid. Niacinamide imbibes large solubilizing power to piroxicam and having approximate solubility 110 mg per gm of melted niacinamide (135°C) whereas aqueous solubility of piroxicam is 0.40 mg/ml at room temperature. Niacinamide does not interfere above 300 nm in the spectrophotometric analysis. Calibration curve of piroxicam was plotted by recording the absorbances of standard solutions of the drug (5, 10, 15, 20 and 25 µg). The absorbances were observed at 358 nm against respective reagent blanks. The percent label claims were found very close to 100.0 (99.08 ±1.764 and 100.93 ±1.303) indicating the accuracy of the proposed method. Percent recoveries estimated by the proposed method are close to 100.0 (99.92 ±1.605 to 101.74 ±1.663) with significant low values of percentage deviation and standard error. Thus, it may be concluded that the proposed method is simple, safe, and precise, and excludes the use of toxic organic solvents.