The IR spectra of 76 dioxin congeners with zero to eight chlorines have been calculated by the DFT (B3LYP) method. Close inspection of the calculated spectra provides a simple rule for LR spectral analysis in polychlorinated dibenzo-p-dioxins (PCDDs). All congeners with a common structural motif of chlorine substitution in either of two benzene rings share the same main IR frequency, and the chlorination of one ring has little influence on the vibrational frequencies of the other ring. As a result, the main ring vibrational frequencies of all dioxin congeners could be classified into 10 groups according to the chlorine substitution pattern. This simplifies the complex IR spectral analysis of PCDDs to identifying two main peaks in essence, each of which corresponds to either of two chlorinated benzene rings. The systematic trend originates from the mass effect of the substituted chlorines. The C-H bending (in plane) character in the ring skeleton vibration mode is affected in quite different ways, depending on whether the chlorine is substituted on longitudinal or lateral positions. In particular, when all the lateral positions (2, 3, 7, 8) are chlorinated in PCDDs, the vibrational frequency of a bl, mode (or its analogues in other symmetry) gives a characteristic IR peak around 1392 cm(-1). This peak is unique to all toxic congeners and could be used as an indicator for them.