Ivanisevic, a serve-and-volley specialist from Croatia, won the 2001 title at the All England Club as a wild-card entry while Martinez, a baseliner from Spain, was the 1994 champion at Wimbledon.
Angelique Kerber and Alexander Zverev both won their singles matches against Spain to give Germany a winning start to their Hopman Cup campaign.
The carnage of seeds at the world's premier grass court tennis tournament continued, with only one of the top 10 women's seeds remaining in the tournament at the fourth round.
Maria Sharapova defeated Hungary’s Timea Babos paving way for her to enter semifinals, where she could meet Spain's Garbine Muguruza.
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