Tan Sri Che Khalib began his career with Messrs Ernst & Young in 1989 and later joined Bumiputra Merchant Bankers Berhad.

Between 1992 and 1999, he served in several companies within the Renong Group. This includes involvement in Projek Lebuhraya Utara Selatan (PLUS), HBN Management Services Sdn Bhd, Renong Overseas Corporation Sdn Bhd and Marak Unggul Sdn Bhd, which is the consortium responsible for the management of Keretapi Tanah Melayu Berhad.

In June 1999, Tan Sri Che Khalib joined Ranhill Utilities Berhad as Chief Executive Officer. He then assumed the position of Managing Director and Chief Executive Officer of KUB Malaysia Berhad. Tan Sri Che Khalib was then appointed as the President/Chief Executive Officer of Tenaga Nasional Berhad (TNB) on 1 July 2004 where he served TNB for eight years until the completion of his contract on 30 June 2012. During his tenure at TNB, Tan Sri Che Khalib drove many improvement initiatives that resulted in TNB becoming one of the success stories in the GLC Transformation Programme. He shaped and set the corporate strategies for TNB when he came up with its 20 year strategic plan in September 2005.

Tan Sri Che Khalib was previously a member of the Board and the Executive Committee of Khazanah Nasional Berhad from year 2000 to 2004. He also served as a Board member within the United Engineers Malaysia (UEM) Group of companies and Bank Industri & Teknologi Malaysia Berhad. He currently sits on the Board of Gas Malaysia Berhad, Zelan Berhad, Malakoff, Johor Port Berhad, MMC Engineering Group Berhad, Aliran Ihsan Resources Berhad, Pos Malaysia Berhad, Bank Muamalat Malaysia Berhad and several private limited companies.

Tan Sri Che Khalib has received many accolades in recognition of his strong leadership including being named Malaysia's CEO of the year in 2008, the highest level of recognition given to corporate leaders in Malaysia, organised by the New Straits Times and American Express. He was also named the CEO of the Year at the inaugural Asia Power and Electricity Awards 2010 and was the recipient of the Lifetime Achievement Award at the Asian Utility Industry Awards 2012.

A qualified accountant, Tan Sri Che Khalib is a member of the Malaysian Institute of Accountants (CA, M) and also a Fellow of the Association of Chartered Certified Accountants (FCCA, UK) United Kingdom.