Many materials used in a wide range of fields consist of polymers that feature great structural complexity. One particularly suitable technique for characterising these complex polymers, that often feature correlated distributions in e.g. microstructure, chemical composition, or molecular weight, is comprehensive two-dimensional liquid chromatography (LC × LC). For example, using a combination of reversed-phase LC and size-exclusion chromatography (RPLC × SEC). Efficient and sensitive LC × LC often requires focusing of the analytes between the two stages. For the analysis of large-molecule analytes, such as synthetic polymers, thermal modulation (or cold trapping) may be feasible. This approach is studied for the analysis of a styrene/butadiene “star” block copolymer. Trapping efficiency is evaluated qualitatively by monitoring the effluent of the trap with an evaporative light-scattering detector and quantitatively by determining the recovery of polystyrene standards from RPLC × SEC experiments. The recovery was dependant on the molecular weight and the temperatures of the first-dimension column and of the trap, and ranged from 46% for a molecular weight of 2.78 kDa to 86% (or up to 94.5% using an optimized set-up) for a molecular weight of 29.15 kDa, all at a first-dimension-column temperature of 80 °C and a trap temperature of 5 °C. Additionally a strategy to reduce the pressure pulse from the modulation has been developed, bringing it down from several tens of bars to only a few bar.