Depends what you mean, or include, in "schema".
If you want to add or drop an index, that can be done "in-flight", although it will require a lock which may halt activity for a time. In the latest Oracle versions, it doesn't need to hold the lock for the entire time it takes to build the index, just for a moment to lock in the change. If you have short-duration transactions it shouldn't be noticeable.
In some cases that applies to tables as well (eg adding a nullable or default column).
If you use PL/SQL (especially packages), things can be a little more complicated. Enhancements were mooted for 11gR1 to enable the in-flight application upgrade, but it got pushed out and is now expected in 11gR2 (probably out first half next year).
In the meantime, a workaround is a multi-schema solution. Say your data sits in one schema ("yellow") and your current application code is running in "blue" schema, you load your new application into "green schema". You switch your connections, one by one, from blue to green. Once your connections are all using "green", you can retire "blue" until your next upgrade (when "blue" becomes the new app and "green" is retired).
If you have a genuine 24/7 system, you'll probably always have to stage some upgrades. For example, add a new column as optional, upgrade the application to set it, then make it mandatory (possibly with some data change script for pre-existing rows).