Background: Invented more than three decades ago by Horning, GC–MS under atmospheric pressure chemical ionization (GC-APCI–MS) has only recently emerged from years of obscurity. However, the general acceptance of GC-APCI–MS is certainly constrained by the lack of spectral libraries, which make the traditional GC–MS approaches so powerful. Results: Here we present a concept of a GC-APCI–QqToF spectral library. The library is web-based, fully searchable and at moment includes spectra of 150 compounds from the most common chemical families. The fragmentation pattern of some chemical families is explained and a protocol for de novo identification has been provided in order to facilitate the identification of unknown compounds. Conclusion: A library for GC-APCI–QqToF is now publicly available online.