1560s, devest (modern spelling is c. 1600), from Middle French devester "strip of possessions," from Old French desvestir, from des- "away" (see dis-) + vestir "to clothe" (see vest (v.)).
The figurative sense of "strip of possessions" is earliest in English; reflexive sense of "to strip oneself of" is from c. 1600. Economic sense (implied in divestment) is from 1955. Related: Divested; divesting.