The semi-final was held on 18 May 2006 at 21:00 (CET). 23 countries performed and all 37 participants and Serbia & Montenegro voted.
| Draw | Country | Language | Artist | Song | Place | Points |
|---|---|---|---|---|---|---|
| 01 | Armenia | English | André | “Without Your Love” | 6 | 150 |
| 02 | Bulgaria | English | Mariana Popova | “Let Me Cry” | 17 | 36 |
| 03 | Slovenia | English | Anžej Dežan | “Mr Nobody” | 16 | 49 |
| 04 | Andorra | Catalan | Jenny | “Sense tu” | 23 | 8 |
| 05 | Belarus | English | Polina Smolova | “Mum” | 22 | 10 |
| 06 | Albania | Albanian | Luiz Ejlli | “Zjarr e ftohtë” | 14 | 58 |
| 07 | Belgium | English, French | Kate Ryan | “Je t’adore” | 12 | 69 |
| 08 | Ireland | English | Brian Kennedy | “Every Song Is a Cry for Love” | 9 | 79 |
| 09 | Cyprus | English | Annet Artani | “Why Angels Cry” | 15 | 57 |
| 10 | Monaco | French, Tahitian | Séverine Ferrer | “La Coco-Dance” | 21 | 14 |
| 11 | Macedonia | English, Macedonian | Elena Risteska | “Ninanajna” (Нинанајна) | 10 | 76 |
| 12 | Poland | English, Polish, Spanish, German, Russian[4] | Ich Troje feat. Real McCoy | “Follow My Heart” | 11 | 70 |
| 13 | Russia | English | Dima Bilan | “Never Let You Go” | 3 | 217 |
| 14 | Turkey | English, Turkish | Sibel Tüzün | “Süper Star” | 8 | 91 |
| 15 | Ukraine | English | Tina Karol | “Show Me Your Love” | 7 | 146 |
| 16 | Finland | English | Lordi | “Hard Rock Hallelujah” | 1 | 292 |
| 17 | Netherlands | English, Imaginary | Treble | “Amambanda” | 20 | 22 |
| 18 | Lithuania | English, French[5] | LT United | “We Are the Winners” | 5 | 163 |
| 19 | Portugal | English, Portuguese | Nonstop | “Coisas de nada” | 19 | 26 |
| 20 | Sweden | English | Carola | “Invincible” | 4 | 214 |
| 21 | Estonia | English | Sandra Oxenryd | “Through My Window” | 18 | 28 |
| 22 | Bosnia and Herzegovina | Bosnian | Hari Mata Hari | “Lejla” | 2 | 267 |
| 23 | Iceland | English | Silvia Night | “Congratulations” | 13 | 62 |