In situ, non-invasive and non-destructive analysis of important artworks and cultural pieces is largely important in art conservation science. Terahertz time-domain spectroscopy and imaging delivers these requirements but lacks a materials database with fundamental understanding of salient pigments, binders and substrates. In this study, the most important synthetic pigments, the copper phthalocyanines, are investigated through terahertz time-domain spectroscopy. The terahertz spectrum reveals a series of characteristic modes in a 0.1–3-THz range across 14 pigment samples. Identification and distinction of copper phthalocyanines’ α, β and ? crystal polymorphs is demonstrated. This uniqueness within the terahertz regime is extended to two halogenated variants and a metal-free form. This invites the use of THz spectroscopy in investigation of contemporary artworks, post 1935, containing these pigments and promotes applications such as identifying fraudulent works of art.