You can, if you know the URL also use the SPFile.Exists property as follows:
using (SPSite site = new SPSite("http://server/site"))
using (SPWeb web = site.OpenWeb())
{
SPFile file = web.GetFile("/site/doclib/folder/filename.ext");
if (file.Exists)
{
...
}
}
One would on first thought assume SPWeb.GetFile throws an exception if the file does not exist. But as you see this is not the case - it will actually return a SPFile object.