An object of the present invention is to provide a pyrroloquinoline quinone tetraalkali salt needing no special reagent, having a high solubility in a solvent, being capable of providing a high-concentration pyrroloquinoline quinone aqueous solution, being hardly changed in color even if being concurrently used with ascorbic acid, and being of a high quality and a high purity; a crystal of a pyrroloquinoline quinone tetrasodium salt; a composition; and a simple method for producing the pyrroloquinoline quinone tetraalkali salt.The pyrroloquinoline quinone tetraalkali salt is represented by the formula (1):wherein M is each independently one selected from the group consisting of Li, K, Na, Rb and Cs.