The advantage of selectivity for coal tar extraction can be obtained by using the solubility parameter of Hansen theory as a guide. However, most of the Hansen solubility parameters (dispersion contributions, (delta)(d); polarity contributions, (delta)(p); hydrogen bonding contributions, (delta)(hb)) of coal tar components (e.g., polycyclic aromatic hydrocarbons, PAHs) were inadequate. This study estimated the Hansen solubility parameters of naphthalene, acenaphthene, anthracene, phenanthrene, pyrene, and fluoranthene from coal tar by applying a new approach regulated by turbidimetric titration and a calculating program based on the method of exhaustion. The extended Hansen approach was used to verify the new approach and evaluate the solubility of the six PAH components in different solvents. The results show that the new method can clearly identify the differences in Hansen solubility parameters caused by various combinations of benzene rings among some isomers (e.g., anthracene and phenanthrene). Among the six PAH compounds, high relativity between their Hansen solubility parameters and solubility data was revealed, indicating an excellent reliability of the new method. An extended Hansen approach is appropriate for the estimation of solubility for the six PAHs with acceptable deviations. Moreover, the relationship between the Hansen solubility sphere and the extended Hansen approach was successfully presented by regression analysis.