What words were used to refer specifically to males before “man” did?

From Etymonline -

'Old English man, mann "human being, person (male or female)'

From Oxford Online (usage note)

'Traditionally the word man has been used to refer not only to adult males but also to human beings in general, regardless of sex. There is a historical explanation for this: in Old English the principal sense of man was ‘a human being’, and the words wer and wif were used to refer specifically to ‘a male person’ and ‘a female person’ respectively. Subsequently, man replaced wer as the normal term for ‘a male person’, but at the same time the older sense ‘a human being’ remained in use.'

http://www.oxforddictionaries.com/definition/english/man

Here's a link to the entry for 'wer' in the Bosworth -Toller Anglo-Saxon Dictionary, which has several definitions:

I. a man, a male person
II. a man, a male that has reached man's estate
III. a being in the form of a man
IV. a married or a betrothed man, a man (as in man and wife), a husband
V. a male

http://bosworth.ff.cuni.cz/035342

We seem to have two references in Beowulf, written sometime between the 8th and 11th centuries:

'se æt Heorote fand wæccendne wer wiges bidan'

which one website translates as 'he found at Heorot a waking man waiting for war

(http://www.as.wvu.edu/english/oeoe/english311/1398.html)

'wonsæli wer weardode hwile', where 'wer' is variously translated as creature or wight:

the unhappy creature occupied for a while
the hapless wight a while had kept

But while Chaucer uses 'wif' quite a lot to mean a woman, and 'man' to mean a man, there doesn't seem to a single instance of 'wer' in the Canterbury Tales (end of 14th century), so it had presumably died out by then.

'Wer' still survives in 'world':

world (n.)
Old English woruld, worold "human existence, the affairs of life," also "a long period of time," also "the human race, mankind, humanity," a word peculiar to Germanic languages (cognates: Old Saxon werold, Old Frisian warld, Dutch wereld, Old Norse verold, Old High German weralt, German Welt), with a literal sense of "age of man," from Proto-Germanic *wer "man" (Old English wer, still in werewolf; see virile) + *ald "age" (see old).

cf etymonline

Then, if this information is correct, "wer" was, at least at some times and places, less specific than "man". Whereas "man" always refered to a person, "wer" could refer to a person or any living thing.

werwolf / werewolf
wergeld / wergelt/ wergild

Now, ‘were’ is noted to for any shapeshifting man-animal. There’s the weretiger ‘A creature of Southeast Asian myth; a shapeshifter who can assume the shape of a tiger.’, and in African myth and folklore, the ‘werehyena’. In syndry myths, fics, and games, there’s the ‘wererat’, the ‘werebear’, the ‘werepanther’, and more.

Werewolf and Weretiger: https://www.youtube.com/watch?v=C45wwS1hUAk

"Wer" comes from a PIE root for man (male person), which is the same that led to "vir" being "man" in Latin, hence words like "virile" in English. "Man" is a Germanic root for person, and it can still be seen in modern German, where it's used like "one" in English:

"Man kann nicht immer gewinnen", lit. "one can not always win", fig. "you win some, you lose some".

Over time "man" came to replace "wer" in English for human male. "Wif", original English for "woman", evolved into "wife", sensibly, and woman derived from a hybrid of those two: wif + man, "female person". Wifman -> wiman -> women.

It's not uncommon across languages that there will be one word for both man and husband, or woman and wife. In Latin, vir meant not only man but also husband (in context, obviously). In Spanish, "mi mujer", literally "my woman", is a totally correct way of saying "my wife", with no implication of sexism whatsoever.