Map your persistent classes with Hibernate Annotations, use EJB3-compatible annotations whenever possible and Hibernate extensions when needed.
Write your data access code with the EJB3 EntityManager API.
All of this runs in plain JSE and does not require EJBs or an application server. However, seriously consider EJB3 session beans though, they are great. Right now the only tested integration of Hibernate Annotations and Hibernate EntityManager is with JBoss EJB3 Application Server. Others will definitely follow.
Wait a few weeks until both Hibernate Annotations and Hibernate EntityManager, and JBoss EJB3, have been updated to the latest Public Final Draft of EJB3 that just came out. Use the time to learn the spec and Hibernate stuff.
Comparable examples of XML mappings and annotations, the most time-consuming issue you will face, can be found in
http://caveatemptor.hibernate.org/ - I recommend staying up-to-date with CVS there.