Yes, the employee may apply for Spouse Supplemental life insurance at any time, however, carrier approval will be required. 

Refer to the Metlife Employee Benefit Plan

Information can be found on the Employee and Retiree Benefits Website under
Supplemental life and accidental death and dismemberment (AD&D) insurance (self-pay) for PEBB employees

To enroll the spouse, the employee may log into the Metlife's My Portal or submit the MetLife Employee Enrollment/Change form directly to MetLife. If the employee submits a paper form and statement of health is required, MetLife will send the statement of health form to the employee.