PHP, 71 chars
for($x=0;++$x<10;print"\n"){for($y=0;++$y<10;){printf("%02d ",$x*$y);}}
Output:
$ php -r 'for($x=0;++$x<10;print"\n"){for($y=0;++$y<10;){printf("%02d ",$x*$y);}}'
01 02 03 04 05 06 07 08 09
02 04 06 08 10 12 14 16 18
03 06 09 12 15 18 21 24 27
04 08 12 16 20 24 28 32 36
05 10 15 20 25 30 35 40 45
06 12 18 24 30 36 42 48 54
07 14 21 28 35 42 49 56 63
08 16 24 32 40 48 56 64 72
09 18 27 36 45 54 63 72 81