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>

If you want to see a complete web application that provides:

• Hibernate configuration through Spring
• DAOs with Spring’s HibernateTemplate
• DTOs with JPA annotations (@Column, @OneToOne, @OneToMany, @ManyToOne etc)
• examples of Hibernate user types for persisting Joda Time and Joda Money

then you might want to refer to the MultiBit Merchant project on GitHub.

It also features examples of RESTful APIs with HAL and uses Dropwizard which may come in useful to you later on when you come to integrate your Hibernate work into a web application. All the code is MIT license so just take it and use it.