Does Detect Evil allow you to detect characters with an evil alignment? Many players would answer that the question is obviously yes, and the answer is 'Yes', but it is not so obvious.
In 3.5, there appear to be 3 designations of evil. There is an "Evil alignment", and "Evil aura", and an "Evil subtype".
The Detect Evil spell clearly tells us that the caster can detect creatures with an "Evil aura", but the PHB also tells us that most characters do not have a good or evil aura. Only clerics and paladins have such an "aura". (PHB 32). There is no "Detect Alignment" or "Know Alignment" spell in the PHB, so I don't think a character can be revealed to be Chaotic Neutral, but characters can be identified as Good/Evil/Lawful, or Chaotic.
I have deduced that "Detect Evil" does reveal any evilly aligned character by looking at the chart on page 219 of the PHB showing "Aura Power". In it, there is a line for "Cleric of an evil deity". Per that line, a 1st level evil cleric would have an aura power of "faint", and a 3rd level evil cleric would have an aura power of "Moderate", and a 5th level evil cleric would have an aura power of "Strong".
Given this clear interpretation, then what is the value of the first line in the chart for "Evil creature"? I deduce that the first line can only apply to creatures that are of evil alignment but that do not have the Evil subtype (line 3) and are not Evil Clerics or Paladins (line 4).
So, a 9th level evil rogue will have a "Faint" "aura power" of evil, the same as a 1st level evil rogue. A 12th level evil rogue will have a "Moderate" "aura power" of evil. Even though rogues do not have auras, they still have "aura powers" for purposes of the detect evil spell.