Dolph moves from building society the Children's Mutual, where he was a marketing consultant.
He has also worked with Citibank, British American Tobacco and Britannia Building Society.
Dolph will be responsible for developing the TNT Mail brand and building awareness of the downstream access service ahead of its launch. TNT Mail will work with Royal Mail, which will deliver post on TNT's behalf.
Before he joined the Children's Mutual, Dolph spent 14 years at HSBC, where he held a number of senior marketing roles.
Dolph said: "This is a unique opportunity to be working for one of the most dynamic new entrants into the UK postal market.
"TNT Mail will be a breath of fresh air for customers to work with as it brings modern thinking to the way mail distribution and delivery operates in this country."
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