This review provides an overview of the biological activities, natural occurrences, and the silver tetrafluoroborate‐ (AgBF4‐) mediated synthesis of proanthocyanidins, glycosides, N‐heterocyclic alkaloid analogues (of pyrrole, morphine, quinoline, isoquinoline, and indole), furan analogues, and halocompounds. AgBF ₄ has been reviewed as an effective reaction promoter, used extensively in the synthesis of relevant biologically active compounds via carbon‐carbon and carbon‐heteroatom bonds formation. The literatures from 1979 to April 2014 were reviewed. Erratum to “Bioactive Phytochemicals: Bioactivity, Sources, Preparations, and/or Modifications via Silver Tetrafluoroborate Mediation” dx.doi.org/10.1155/2015/423734