Да пути вроде правильные.
config.php
<?php
// DIR
define('DIR_APPLICATION', 'W:\home\opencart.local\www/catalog/');
define('DIR_SYSTEM', 'W:\home\opencart.local\www/system/');
define('DIR_DATABASE', 'W:\home\opencart.local\www/system/database/');
define('DIR_LANGUAGE', 'W:\home\opencart.local\www/catalog/language/');
define('DIR_TEMPLATE', 'W:\home\opencart.local\www/catalog/view/theme/');
define('DIR_CONFIG', 'W:\home\opencart.local\www/system/config/');
define('DIR_IMAGE', 'W:\home\opencart.local\www/image/');
define('DIR_CACHE', 'W:\home\opencart.local\www/system/cache/');
define('DIR_DOWNLOAD', 'W:\home\opencart.local\www/download/');
define('DIR_LOGS', 'W:\home\opencart.local\www/system/logs/');
// DB
define('DB_DRIVER', 'mysql');
define('DB_HOSTNAME', 'localhost');
define('DB_USERNAME', 'test');
define('DB_PASSWORD', 'test');
define('DB_DATABASE', 'opencart');
define('DB_PREFIX', 'oc_');
?>
admin/config.php
<?php
// HTTP
define('HTTP_SERVER', 'http://195.138.66.234/admin/');
define('HTTP_CATALOG', 'http://195.138.66.234/');
define('HTTP_IMAGE', 'http:/195.138.66.234/image/');
// HTTPS
define('HTTPS_SERVER', 'http://195.138.66.234/admin/');
define('HTTPS_IMAGE', 'http://195.138.66.234/image/');
// DIR
define('DIR_APPLICATION', 'W:\home\opencart.local\www/admin/');
define('DIR_SYSTEM', 'W:\home\opencart.local\www/system/');
define('DIR_DATABASE', 'W:\home\opencart.local\www/system/database/');
define('DIR_LANGUAGE', 'W:\home\opencart.local\www/admin/language/');
define('DIR_TEMPLATE', 'W:\home\opencart.local\www/admin/view/template/');
define('DIR_CONFIG', 'W:\home\opencart.local\www/system/config/');
define('DIR_IMAGE', 'W:\home\opencart.local\www/image/');
define('DIR_CACHE', 'W:\home\opencart.local\www/system/cache/');
define('DIR_DOWNLOAD', 'W:\home\opencart.local\www/download/');
define('DIR_LOGS', 'W:\home\opencart.local\www/system/logs/');
define('DIR_CATALOG', 'W:\home\opencart.local\www/catalog/');
// DB
define('DB_DRIVER', 'mysql');
define('DB_HOSTNAME', 'localhost');
define('DB_USERNAME', 'test');
define('DB_PASSWORD', 'test');
define('DB_DATABASE', 'opencart');
define('DB_PREFIX', 'oc_');
?>