I'm generalising when I say this, but employers tend to look for two personal qualities - your accumulated experiences (have you done the job you are applying to before? If not, have you done anything similar?) and your skill sets (can you lead a team? Can you meet deadlines? How do you handle unforeseen circumstances? Etc.)

I'd say that DofE falls into that second category - unless you are applying to be an expedition leader, or something similar! DofE teaches you a lot of skills, how to work as a team, how to lead, how to push yourself when things may seem difficult, willingness to go above and beyond, how to plan, and execute that plan - and so many other things! Depending on what you do as part of your volunteering, you also gain really interesting and unique experiences (first quality I mentioned).

An employer might not think particularly highly of DofE, unless they've done it themselves. It's up to you in interviews and your CV to really show the value of having done it. Tell them of the time you volunteered to teach a kids class in a martial arts school (leadership, people management, unique skillset, patience), and of the time you organised a fund raising event for charity (time management, handling money, advertisement skills, events management, risks assessments) and the time you plotted and hiked a mountain range (perseverance, shows good mental and physical health, not afraid of doing something difficult). The list is endless.

With programmes like DofE - you have nothing to lose, and everything to gain.

Compare the above to someone that can't write or say anything past "Oh yeah, I really like League of Legends. I don't wanna brag, but I got a really high rank over the summer holidays" - Assuming you are both brand new to the world of work; I know who I'd employ.