In this work, it has been extended to methanol:water mobile phases, the use of a background correction method for on-line LC-FTIR measurements named Univariate background correction based on the use of a reference spectra Matrix (UBC-RSM) and absorbance ratios. It permits to overcome the problem related to spectral changes occurring during the gradient elution, which in the past limited the on-line coupling of LC and FTIR to isocratic elutions. The combined use of the aforementioned background correction technique in on-line isocratic and gradient LC-FTIR, and partial least squares (PLS) has been applied for the search of the critical conditions for polymers. Polyethylen glycol (PEG) has been used as a model example and results found fitted well with previously published ones. (c) 2008 Elsevier B.V. All rights reserved.