Exemption from EPF for a particular employee is not possible. If the employer is having better schemes than what are offered by EPFO, then the establishment may be exempted from EPF. At the same time if the employee concerned is a new employee (joined some time after 1st Sept 2014) who had no existing PF account then he can be excluded from PF provided his salary is more than Rs 15000. For an existing member cannot get excluded from PF.
(Why should an employee chose to be out of EPF? When no other agency, Bank, nothing, is giving an interest higher than what is offered by EPFO why should an employee say that he would like to go out of EPF?)