ABSTRACT At optical/ultraviolet energies, blazars display an underlying thermal (unpolarized) contribution from the accretion disc, torus, and line-emitting regions, diluting the polarized emission from the jet-component. Optical polarimetry can be used to disentangle the thermal and non-thermal components, and place constraints on the particle populations and acceleration mechanisms responsible for the non-thermal emission. We present the results of a linear optical spectropolarimetric observing campaign of 18 blazars (six BL Lac-type objects and 12 flat-spectrum radio quasars) undertaken with the Southern African Large Telescope between 2016 and 2022. This was done to observe these systems during flaring states, as well as long-term monitoring of PKS1510-089, AP Lib, and PKS 1034-293. The observations traced the frequency dependence of the degree and angle of polarization, as well as changes in the spectral line strengths. We investigated possible correlations between the polarization and other observed characteristics for the sources. While an indication of correlation was found between the frequency dependence and the average level of polarization for some sources, a correlation was not found for the population as a whole. These results highlight that continuous observations and in-depth modelling of polarization and its frequency dependence is required to obtain a more holistic view of TeV blazars.