Iceland, the lowest-ranked team in the play-offs, must beat Croatia to reach their first ever major tournament, while Greece meet Romania.
The two-legged ties will be played on 15 November and 19 November.
The eight nations all finished second in the qualifying groups, with 1998 World Cup winners France runners-up to current holders Spain in Group I.
Ukraine were beaten to automatic qualification by Group H rivals England.
Portugal, Greece, Croatia and Ukraine were the four seeded teams in the draw which took place on Monday.
The four teams that qualify will complete a total of 13 European nations at the tournament in Brazil.
Tough draw for Portugal and France. Hopefully Paulo Bento will get out of his own way long enough for Portugal to make it through.