spoolsv.exe is a Microsoft Windows system executable which handles the printing process to your local printers. It useally only asks for access if you a network of PC's using the same printer on the network. That said...there is also a trojan that uses a same name file which is used to excute the trojans instructions.
I would recommend you download hijackthis and post your log in our hijackthis section so we can go through it for you..and make sure this file is running from it's correct location. (c:\windows\System32 folder)