To enable centos-dev, you need to create /etc/yum.repos.d/centos-test.repo and add the following
[c5-testing] name=CentOS-5 Testing baseurl=http://dev.centos.org/centos/5/testing/$basearch/ enabled=1 gpgcheck=1 gpgkey=http://dev.centos.org/centos/RPM-GPG-KEY-CentOS-testing
Then when you
yum update php
You will get the latest version. Please note it breaks ioncube and you will need to download the latest version from http://www.ioncube.com/loaders.php
Thanks to this comment for showing the way.
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