"clothing designed to be worn outside other garments," 1921, from outer (adj.) + wear (n.), probably based on underwear.
Entries linking to outerwear
outer adj.
"that is farther out, that is exterior or external; of or pertaining to the outside; further removed," late 14c., comparative of out (on analogy of inner), replacing by 18c. forms descended from Old English uttera (comparative of Old English ut "out") which developed into utter (adj.) and was no longer felt as connected with out. Outer space "region beyond the earth's atmosphere" is attested from 1845.
wear n.
"action of wearing" (clothes), mid-15c., from wear (v.). Meaning "what one wears" is 1560s. To be the worse for wear is attested from 1782; noun phrase wear and tear is first recorded 1660s, implying the sense "process of being degraded by use."