Not really these days, at least for DofE, since everyone and their mum does it, it's become fairly meaningless as far as uni applications go. General volunteering is also usually not directly relevant to academic study at uni level.
It can be construed in a relevant way depending on the course you're applying to if you focus on the development of transferable skills in those activities, and then apply these to your proposed degree programme. But equally there are plenty of other ways you could develop those same skills, so the fact it's DofE or volunteering makes no odds.
Basically, do it if you want to do it for your own personal gratification or interest, don't do it just because you think it'll help you get into uni - it won't. Same goes for the EPQ, for that matter (although that does sometimes affect admissions as some unis give lower offers to those with a good EPQ result, but you still shouldn't do it unless you have a clear idea for a project at the outset rather than just doing it "because").