We developed a modified paper spray ionization (PSI) platform, named as paper cone spray ionization (PCSI), for direct mass spectrometric analysis of raw solid samples. The major modification from conventional PSI was the geometry of the paper base: PCSI uses a triangular-pyramidal-shaped paper tip instead of a planar triangular-shaped one. This three-dimensional paper cone serves as a sample container, an in situ solid–liquid extraction chamber, an analyte transport channel, as well as an electrospray tip. Unlike conventional PSI mass spectrometry (MS), a weighing paper with relatively low permeability was found to be more suitable for PCSI MS than other papers. PCSI MS rapidly generated major chemical fingerprints from various solid materials including powdered tablets as well as raw and processed food materials without any sample pre-treatment.