A set of 460 Indian coal samples has been used to establish correlations between volatile matter percentage yield (%VMdmmf) and compositional parameters, such as the weight percentages of Carbon (Cw), Hydrogen (Hw) and Oxygen (Ow); atomic ratios of the H/C, O/C and H/C; and atomic percentages of Carbon (Ca), Hydrogen (Ha) and Oxygen (Oa). Based on dry, mineral-matter-free (dmmf) basis wt% volatile matter is estimated according to the following expression. %V-(dmmf) = 20.3651 - 0.4042*Cw + 8.4668*Hw + 0.7183*Ow (2) %V-(dmmf) = -18.9489 - 68.1232*O/C + 93.7718*O/H + 68.8461*H/C (4) %VMdmmf = 144.7350 - 1.9846*Ca (6) %Vm(dmmf) = -15.4975 - 0.3667*Ca + 1.6272*Ha + 1.6192*Oa (7) The standard error of estimate and correlation coefficients of the developed correlations [Eqs. (2), (4), (6) and (7)] are found to be 1.73; 0.93, 1.74; 0.93, 1.74; 0.93 and 1.72; 0.93 (dmmf) basis respectively.