EDLI applies to all the employees contribute to PF. Though there is no minimum service for getting the amount prescribed under EDLI, the employee should be an active member. Since the death has happened on the same day or second of of joining EPF, it is a legal question, in fact. At the same time, if the employee was already a member of PF in his earlier organisation, then he should have a contribution history. Then his dependents would get the benefits of EDLI. On the other hand, if he is a new employee not yet contributed to PF at all, the question of applicability will arise.
The EDLI being an insurance linked to deposit (in PF), the amount is calculated based on his PF accumulations for the last one year. The maximum amount admissible is Rs 7 lakhs.
I presume by WC Policy, you mean Workmen Compensation Policy. The Workmen (Employees) Compensation applies only if the employee dies in an accident or employment injury during the course of employment. The Policy will not cover any normal deaths.