PHP will let you build the pages of your site that make up your video conferencing and chat applications, but it won't deliver or stream video for you - PHP runs on the server only and renders out HTML to a client browser.
For the video, the first thing you'll need is a live streaming account with someone like akamai or the numerous others in the field. Using this account gives you an ingress point for your video - ie: the server that you will stream your live video up to.
Next, you want to get your video out to the browsers - windows media player, flash or silverlight will let you achieve this - embedding the appropriate control for your chosen technology into your page (using PHP or whatever) and given the address of your live video feed.
PHP (or other scripting language) would be used to build the chat part of the application and bring the whole thing together (the chat and the embedded video player).
Hope this helps.