Rubinstein's appointment follows last week's launch of the Palm Pre, a new smartphone being touted as the first worthy competitor to the Apple iPhone.
Rubinstein, who joined Palm as executive chairman in October 2007 to help bring innovation back to the company, assumes his new role on June 12.
He previously worked for Apple as head of hardware engineering, overseeing the development of the iMac and the iBook, as well as the iPod.
Before joining Apple, Rubinstein worked for a variety of computer companies, including Hewlett-Packard and Next, and started his own firm, Firepower Systems.
He is one of a number of former Apple employees now at or associated with Palm including Mike Bell, a long time former senior VP for product development at Apple.
Rubinstein said: "I am very excited about taking on this expanded role at Palm. Ed and I have worked very hard together the past two years, and I'm grateful to him for everything he's done to help set the company up for success.
"With Palm webOS we have ten-plus years of innovation ahead of us, and the Palm Pre is already one of the year's hottest new products. Due in no small part to Ed's courageous leadership, we're in great shape to get Palm back to continuous growth, and we plan to keep the trajectory going upward."
Colligan, who has been Palm's chief executive since 2005, joined the company in 1993. He will be joining Elevation Partners, which acquired 25% of Palm two years ago.
Colligan said: "I'm very proud of what Palm has accomplished so far. We pioneered two major product categories and I believe we are on our way to defining the standard for the mobile web."
The reportedly sold over 100,000 in 48 hours.
It is priced at $199 for an eight-gigabyte model after a $100 rebate, making it more expensive than the iPhone 3G, which Apple lowered to $99 on Monday.
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