The self-modeling curve resoln. (SMCR) technique called orthogonal projection approach (OPA) was used to resolve a complex set of Fourier transform (FT)-Raman spectra acquired online during styrene/1,3-butadiene block-copolymn. The routine application of OPA did not yield phys. acceptable results and manual corrections of the erroneous parts of the styrene concn. profiles had to be employed to improve the resolved spectra and concns. of the two monomers and polybutadiene. The failure of automatic resoln. by OPA is due to the ambiguity of SMCR. This problem is convincingly illustrated in the present case wherein is shown that phys. reasonable manual correction significantly improve the results. The present study demonstrates that the combination of an automatic method for curve resoln. and a suitable, efficient spectroscopic set-up enables real-time monitoring of this industrially important polymer reaction better than any conventionally employed technique.