Modifications of integrated calibration method (ICM) in its basic variant and complementary dilution method version (CDM) were adapted to multi-component (MC) analysis to obtain novel calibration approaches improving the accuracy of analytical results. Methods were developed conceptually and their performance was assessed on the basis of polycyclic aromatic hydrocarbons (PAHs) determination in air samples. The natural (thuja needles) and synthetic (polymer) materials were combusted simulating fires or home users’ combustion. Analytical method for determination EPA PAHs was developed using HPLC-DAD-FLD. It has been confirmed that the improved analytical results accuracy obtained in MC-ICM and MC-ICM/CDM was described by relative error < 1.5%. Multiplicative effects due to the coelution of other substances were detected by comparing the individual estimations of the analytical results. The results free from this effect were determined. According to RGB Additive Color Model, the proposed approach is White – method is a good candidate of choice for all applications.