Goldsmith has global responsibility for HR and internal communications and will report directly to chairman and co-founder Aneel Bhusri.
Prior to joining Workday, Goldsmith served as CHRO and executive vice president at video conferencing firm Polycom.
Goldsmith said: "It's evident that Workday's success is fueled by a commitment to quality and engagement when it comes to an organization's most valuable asset - its people.
"I'm thrilled to be part of a company with such dedication to the value HR can infuse into the overall business, and look forward to advancing current efforts while establishing new goals to support our growth."
Bhusri said: "With more than 2,400 employees and an exciting growth plan, Workday's focus on employee development, programs, and recruitment has never been more important than it is today,
"Ashley is an incredible addition to the Workday leadership team, and we look forward to her guidance as we continue to open offices and attract top talent around the world."
