If a couple is expecting a child, and they both are eligible for Paid Family Leave, yes, they can both take PFL for bonding. If they work for different companies, they can both take leave at the same time, take it consecutively, or find an alternating pattern that works best for them.
For example, Mom could take off Fridays and Dad Mondays, leaving only 3 days a week for other child care arrangements.
If both parents work for the same company, it will be up to the employer to decide if they will allow the couple to take Paid Family Leave at the same time, or if they prefer the couple to take it consecutively. If you fall into this category, check with your employer to see how they intend to handle such cases so you can plan accordingly.