Australia have won the women's team competition seven times, second only to the United States, but their last win came in 1974 and they last reached the final back in 1993.
Under Taylor's seven-year reign they got back into the elite world group and the 31-year-old Molik's first tie in charge will be against champions Czech Republic in Europe next month.
"Dave has left big shoes to fill and I am really inspired by the challenge," Molik said. "It is an exciting time in Australian tennis and we have the talent in this team to produce some great results."
