Left Join With Where Clause

The where clause is filtering away rows where the left join doesn't succeed. Move it to the join:

SELECT  `settings`.*, `character_settings`.`value`
FROM    `settings`
LEFT JOIN 
       `character_settings` 
ON     `character_settings`.`setting_id` = `settings`.`id`
        AND `character_settings`.`character_id` = '1'  

When making OUTER JOINs (ANSI-89 or ANSI-92), filtration location matters because criteria specified in the ON clause is applied before the JOIN is made. Criteria against an OUTER JOINed table provided in the WHERE clause is applied after the JOIN is made. This can produce very different result sets. In comparison, it doesn't matter for INNER JOINs if the criteria is provided in the ON or WHERE clauses -- the result will be the same.

  SELECT  s.*, 
          cs.`value`
     FROM SETTINGS s
LEFT JOIN CHARACTER_SETTINGS cs ON cs.setting_id = s.id
                               AND cs.character_id = 1