Based on position group contribution additivity, a new simple and reliable method is proposed for the prediction of critical temperatures of organic compounds involving a carbon chain from C2 to C 18. Contributions for organic compounds containing oxygen, nitrogen, chlorine, bromine, and sulfur are given. The overall average absolute difference for critical temperature T-c predictions of 467 organic compounds is 6.6 K and 1.1%, which means absolute relative difference, which is compared to 17.6 K and 3.1% with the method of Joback and Reid and 13.5 K and 2.3% with the method of Constantinou and Gani. Owing to the utilization of the position compensation factor, this method demonstrates significant improvements compared to the previously used first- or second-order method, especially in the capability of distinguishing between isomers. Furthermore, this new position contribution group method with better precision and simplicity is fully predictive.