This article discusses the potential of self-modeling curve resolution analysis (SMCR) for the evolution of on-line vibrational spectral data of polymerisation and transesterification. After the general introduction of the SMCR approach, representative SMCR techniques like orthogonal projection analysis (OPA) and simple-to-use interactive self-modeling mixture analysis (SIMPLISMA) are briefly outlined. As examples the SMCR analysis of the Raman spectra of the block copolymerisation of styrene and 1,3-butadiene and that of the near-infrared (NIR) spectra of the melt-extrusion transesterification of ethylenevinylacetate copolymer will be illustrated. In the last part of this review paper, a new powerful SMCR method that we have recently proposed is demonstrated.