No there is no difference when you setup Hibernate either way. Using maven or ant will only change the way you configure, build, deploy your project.
The way you write Hibernate code will not change in any way if you use Maven or Ant.
In maven pom.xml you will have to add the repository as documented below -
<dependency>
<groupId>org.hibernate</groupId>
<artifactId>hibernate-core</artifactId>
<version>4.0.1.Final</version>
</dependency>
<dependency>
<groupId>org.hibernate</groupId>
<artifactId>hibernate-validator</artifactId>
<version>4.2.0.Final</version>
</dependency>
<dependency>
<groupId>org.hibernate.common</groupId>
<artifactId>hibernate-commons-annotations</artifactId>
<version>4.0.1.Final</version>
<classifier>tests</classifier>
</dependency>
<dependency>
<groupId>org.hibernate.javax.persistence</groupId>
<artifactId>hibernate-jpa-2.0-api</artifactId>
<version>1.0.1.Final</version>
</dependency>
<dependency>
<groupId>org.hibernate</groupId>
<artifactId>hibernate-entitymanager</artifactId>
<version>4.0.1.Final</version>
</dependency>
<dependency>
<groupId>javax.validation</groupId>
<artifactId>validation-api</artifactId>
<version>1.0.0.GA</version>
<scope>provided</scope>
</dependency>
<dependency>
<groupId>org.slf4j</groupId>
<artifactId>slf4j-api</artifactId>
<version>1.6.4</version>
</dependency>
<dependency>
<groupId>org.jboss.logging</groupId>
<artifactId>jboss-logging</artifactId>
<version>3.1.0.CR2</version>
</dependency>
<dependency>
<groupId>org.slf4j</groupId>
<artifactId>slf4j-log4j12</artifactId>
<version>1.6.4</version>
</dependency>
And the following repository will have to be added -
<repository>
<id>JBoss</id>
<name>JBoss Repsitory</name>
<layout>default</layout>
<url>http://repository.jboss.org/maven2</url>
</repository>