The effects of different variables for analyte-matrix interactions on supercritical fluid extraction (SFE) efficiencies of polycyclic aromatic hydrocarbons (PAHs) were investigated. The results indicated that the main factors for describing a matrix, e.g., the chemical properties of the matrix surface, surface area, and pore size, could significantly influence the analyte-matrix interactions. The polarizability of an analyte was demonstrated to be yet another significant factor for influencing analyte-matrix interactions. Either elevating the temperature or adding modifiers could also increase the SFE recoveries. The underlying mechanisms of these variables are discussed.