1868, earlier alla capella (1824), from Italian, "in the style of Church music, in the manner of the chapel," literally "according to the chapel," from cappella "chapel" (see chapel). Originally in reference to older church music (pre-1600) which was written for unaccompanied voices; applied 20c. to unaccompanied vocal music generally. Italian a is from Latin ad "to, toward; for; according to" (see ad-); alla is a la "to the." Sometimes in the Latin form a capella.
Also denoting "that instruments are to play in unison with the voices, or that one part is to be played by a number instruments." ["Chambers's' Encyclopaedia," 1868]
You are not the first person puzzled by the expression "A Capella," or, at any rate, unable to understand it should signify the exact reverse of what it literally does signify. The chorales in oratorios were invariably accompanied, either by double-bass or the whole band. Hence they were, with perfect correctness, said to be performed "a capella." But, as other chorales, sung as part of the church service, were written in the same and simple style the expression "a capella" came in time to be applied to them also, despite their being sung without any instrumental accompaniment whatever. [The Music World, Sept. 11, 1875]