I assume you know how to develop a facebook application

This code below can upload your photo to Profile Pictures album via Facebook application

require_once('fbconfig.php');
try
	{
		include_once("facebook.php");
	}
	catch(Exception $c)
	{
		echo '';
		print_r($o);
	}

	$uid = NULL; //facebook user id

	$facebook = new Facebook(array(
           'appId'  => $fbconfig['appid'],
           'secret' => $fbconfig['secret'],
           'cookie' => true
    	    ));

	$session = $facebook->getSession(); //getting username of logged in user

	$login_url = $facebook->getLoginUrl(
        	array(
		'canvas'    => 1,
            	'fbconnect' => 0,
                'req_perms' => 'read_stream,publish_stream,photo_upload,user_photos,user_photo_video_tags'
        	)
	);

if ($session) {
        $facebook->setFileUploadSupport(true); // upload feature ON

        $albums = $facebook->api('/me/albums/'); // getting facebook albums of user

        foreach ($albums['data'] as $album) {
            if($album['type'] == 'profile'){
                $album_uid = $album['id'];
            }
        }

        $photo_details = array(
            'message'=> 'uploaded via application'
        );
        $file = 'photo.jpg';
        $photo_details['image'] = '@' . realpath($file);

		print_r($photo_details); 

        $upload_photo = $facebook->api('/'.$album_uid.'/photos', 'post', $photo_details);

        echo 'View my photo';
}
else {
       	echo "";
        exit;
}