Mediation is an interesting process in divorce, because there are so many issues in divorce and some of them lend themselves to being mediated and some don't. Custody issues, visitation issues, and issues regarding children are very personal and can be mediated very easily because they don't run on hard and fast rules. How you and your spouse want to parent your children can be agreed upon and put into a parenting agreement. Mediation is a wonderful tool to resolve those kinds of disputes.
When it comes to financial issues, it gets a little bit more complicated. However, mediation can be very effective in family law situations when it comes to financial issues, provided that both parties are on the same footing. If both of you have equal knowledge as to your assets and income and if each of you has somewhat of the same level of sophistication as to the financial aspects of your life, mediation with an attorney or a former judge who is familiar with your jurisdiction's divorce laws can be very helpful in handling the financial issues.
Divorce mediation is not helpful at the beginning of a case if one spouse has all of the knowledge and the other spouse doesn't. I have clients come to me regularly with situations where their spouse is the bully and wants to do mediation, but what they're really looking for is a forum to continue to beat up on my client and get what they want. So until you're confident that you know what the issues are or until you participate in a mediation process where you can be represented by your attorney at that time, my advice to people is to not mediate.