We describe a technique, differential temperature laser induced fluorescence (DT-LIF), and an analytical algorithm, structure-based cross correlation (SBCC), that are capable of separating overlapping cold and hot bands in a laser induced fluorescence (LIF) spectrum. DT-LIF/SBCC is illustrated by application to a pair of synthetic spectra, and is demonstrated by application to a segment of an experimental acetylene (A) over tilde-(X) over tilde spectrum. The goal is to identify and separate hot and cold band spectral features numerically, prior to any attempt at assignment of the raw spectrum. The DT-LIF/SBCC combination is shown to be a useful tool for disentangling hot and cold band spectra. (c) 2006 Elsevier B.V. All rights reserved.