I do not think this information is available. But with some testing it should be pretty easy.
If you only need UILabel in the entire toolbar, I would suggest just adding it to the UIToolbar , which is a subclass of UIView . You do not need all the functions of UIBarButtonItem in your case .... only the background that I assume.
Then set UILabel.frame (with the fields you want) + addSubview: + a UITextAlignmentCenter should do the job! Plus, perhaps also autoresizingMask with UIViewAutoresizingFlexibleWidth | UIViewAutoresizingFlexibleHeight UIViewAutoresizingFlexibleWidth | UIViewAutoresizingFlexibleHeight if you control device orientation ...
EDIT 1 :
Since there are some doubts about this suggestion, I did a quick test:
UILabel *label = [[[UILabel alloc] initWithFrame:CGRectMake(10, 0, 300, 44)] autorelease]; label.text = @"Hello world"; label.textAlignment = UITextAlignmentCenter; label.textColor = [UIColor whiteColor]; label.shadowColor = [UIColor blackColor]; label.backgroundColor = RGBACOLOR(255, 0, 0, .3f); [self.toolbar addSubview:label];
Here is the result:

EDIT 2 :
Now that I have run Xcode and written the code, it is easy to understand your main question. By slightly changing the previous code:
UILabel *label = [[[UILabel alloc] initWithFrame:CGRectMake(0, 0, 320, 44)] autorelease]; ... same [self.toolbar setItems: [NSArray arrayWithObject: [[[UIBarButtonItem alloc] initWithCustomView:label] autorelease]]];
brings the following:

So, you guessed it, there is a 12px left edge, but custom views are not like their size being resized to fit, so in this case there is no right edge ... unless you resize your view accordingly.
EDIT 3 :
If your UILabel doesn't need a background, here's what I will probably do (which is for UIBarButtonSystemItemFlexibleSpace for everyone ...):
UILabel *label = [[[UILabel alloc] init] autorelease]; label.text = @"Hello world"; ... same [label sizeToFit]; [self.toolbar setItems: [NSArray arrayWithObjects: [[[UIBarButtonItem alloc] initWithBarButtonSystemItem:UIBarButtonSystemItemFlexibleSpace target:nil action:nil] autorelease], [[[UIBarButtonItem alloc] initWithCustomView:label] autorelease], [[[UIBarButtonItem alloc] initWithBarButtonSystemItem:UIBarButtonSystemItemFlexibleSpace target:nil action:nil] autorelease], nil]];
Result:

EDIT 4 :
As a side, no, after working more on UIToolbar , 12px is the default space added before the button was clicked. And I just found it funny, delimiters work with negative values! . I.E. if you need 2px space between two buttons just add -10px UIBarButtonSystemItemFixedSpace ... Handy!