1520s, "sharp or stinging to the feelings" (a sense now obsolete), from Middle French piquant "pricking, stimulating, irritating," present participle of piquer "to prick, sting, nettle" (see pike (n.1)). From 1640s as "of agreeable pungency or sharpness of taste or flavor;" by 1690s as "of smart, lively, or racy nature." Related: Piquantly.
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