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MySQL 5.4 Reference Manual :: 9 Internationalization and Localization :: 9.1 Character Set Support :: 9.1.13 Character Sets and Collations That MySQL Supports
9.1.13.1 Unicode Character Sets »
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9.1.13. Character Sets and Collations That MySQL Supports

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9.1.13.1. Unicode Character Sets
9.1.13.2. West European Character Sets
9.1.13.3. Central European Character Sets
9.1.13.4. South European and Middle East Character Sets
9.1.13.5. Baltic Character Sets
9.1.13.6. Cyrillic Character Sets
9.1.13.7. Asian Character Sets

MySQL supports 70+ collations for 30+ character sets. This section indicates which character sets MySQL supports. There is one subsection for each group of related character sets. For each character set, the allowable collations are listed.

You can always list the available character sets and their default collations with the SHOW CHARACTER SET statement: 

mysql> SHOW CHARACTER SET;
+----------+-----------------------------+---------------------+
| Charset  | Description                 | Default collation   |
+----------+-----------------------------+---------------------+
| big5     | Big5 Traditional Chinese    | big5_chinese_ci     |
| dec8     | DEC West European           | dec8_swedish_ci     |
| cp850    | DOS West European           | cp850_general_ci    |
| hp8      | HP West European            | hp8_english_ci      |
| koi8r    | KOI8-R Relcom Russian       | koi8r_general_ci    |
| latin1   | cp1252 West European        | latin1_swedish_ci   |
| latin2   | ISO 8859-2 Central European | latin2_general_ci   |
| swe7     | 7bit Swedish                | swe7_swedish_ci     |
| ascii    | US ASCII                    | ascii_general_ci    |
| ujis     | EUC-JP Japanese             | ujis_japanese_ci    |
| sjis     | Shift-JIS Japanese          | sjis_japanese_ci    |
| hebrew   | ISO 8859-8 Hebrew           | hebrew_general_ci   |
| tis620   | TIS620 Thai                 | tis620_thai_ci      |
| euckr    | EUC-KR Korean               | euckr_korean_ci     |
| koi8u    | KOI8-U Ukrainian            | koi8u_general_ci    |
| gb2312   | GB2312 Simplified Chinese   | gb2312_chinese_ci   |
| greek    | ISO 8859-7 Greek            | greek_general_ci    |
| cp1250   | Windows Central European    | cp1250_general_ci   |
| gbk      | GBK Simplified Chinese      | gbk_chinese_ci      |
| latin5   | ISO 8859-9 Turkish          | latin5_turkish_ci   |
| armscii8 | ARMSCII-8 Armenian          | armscii8_general_ci |
| utf8     | UTF-8 Unicode               | utf8_general_ci     |
| ucs2     | UCS-2 Unicode               | ucs2_general_ci     |
| cp866    | DOS Russian                 | cp866_general_ci    |
| keybcs2  | DOS Kamenicky Czech-Slovak  | keybcs2_general_ci  |
| macce    | Mac Central European        | macce_general_ci    |
| macroman | Mac West European           | macroman_general_ci |
| cp852    | DOS Central European        | cp852_general_ci    |
| latin7   | ISO 8859-13 Baltic          | latin7_general_ci   |
| cp1251   | Windows Cyrillic            | cp1251_general_ci   |
| cp1256   | Windows Arabic              | cp1256_general_ci   |
| cp1257   | Windows Baltic              | cp1257_general_ci   |
| binary   | Binary pseudo charset       | binary              |
| geostd8  | GEOSTD8 Georgian            | geostd8_general_ci  |
| cp932    | SJIS for Windows Japanese   | cp932_japanese_ci   |
| eucjpms  | UJIS for Windows Japanese   | eucjpms_japanese_ci |
+----------+-----------------------------+---------------------+

In cases where a character set has multiple collations, it might not be clear which collation is most suitable for a given application. To avoid choosing the wrong collation, it can be helpful to perform some comparisons with representative data values to make sure that a given collation sorts values the way you expect.

Collation-Charts.Org is a useful site for information that shows how one collation compares to another.