Laser multiphoton ionization (LMPI) and laser-induced fluorescence (LIF) techniques were simultaneously applied to analysis of polycyclic aromatic hydrocarbons (PAH) in apolar solution. This combination of singlephoton (LIF) and multiphoton (LMPI) processes provides unique information which is shown to be sufficient for both identification and quantification of PAH molecules in simple mixtures. We suggest 3D calibration plots (concentration as a function of both LMPI and LIF signals) where each PAH compound is represented by a unique vector in this space. The projections of such vectors onto the LMPI-LIF plane are the basis of PAH analysis, where only two measurements (LMPI and LIF signals) are required for speciation and quantification of a single component. A geometrical algorithm for decomposition of simple PAH mixtures, is also addressed.Many polycyclic aromatic compounds are classified as carcinogenic or mutagenic; therefore, these molecules and their derivatives are of considerable environmental interest. [1][2][3] They are produced in many industrial processes when incomplete fuel combustion takes place. The long-range global transport of polycyclic aromatic hydrocarbon (PAH) compounds, as well as local industrial process control, requires screening and real-time monitoring. Reliable and simple in their operational mode techniques, which offer remote or on-line chemical information, they are still of current analytical interest.There are several well-established analytical procedures for PAH analysis, most of them based on GC/MS (for the low-mass and volatile compounds) and HPLC/MS (for the higher molecular masses). These laboratory methods are accurate and can handle quite complicated mixtures. However, they are both expensive and time-consuming; therefore, new low-cost or on-line techniques are needed.