In this study, a combined approach of group contribution and position distribution function is presented to estimate the critical volume of a variety of pure organic compounds involving a carbon chain from C2 to C18. The results indicate that our model provides very satisfactory results, and the deviation from the most reliable experimental data is not more than 2.1 %. The overall average absolute difference for critical volume V-c predictions of 219 organic compounds is 8.8 cm(3).mol(-1) and 2.1 % means relative derivation, which is compared to 26.5 cm(3).mol(-1) and 6.0 % with the method of Joback and 23.5 cm(3).mol(-1) and 5.6 % with the method of Constantinou. and Gani. The higher prediction accuracy of the proposed method shown in our previous works and this work suggests that it is possible to use a similar framework to predict the three critical properties, T-c, P-c and V-c of organic compounds containing various functionalities.