Nope. Pumpout might be able to pull in a little air through the toilet--in fact, a hissing sound from the toilet during pumpout is a big clue that the vent is blocked--but not enough for the toilet to replace the tank vent during pumpout. The best it can do is let enough air escape to relieve the pressure in the tank,which will take some time.
TANK VENTS 101
All tank vents have two main functions: to provide an escape for air displaced by incoming contents and provide a source of air to replace contents as they're pulled out. When air displaced by incoming waste cannot escape out the vent the tank becomes pressurized, creating increasing back pressure that prevents the toilet from flushing.
Without a source of air to replace contents as they're being sucked out of the tank, the pump will pull a vacuum that'll prevent it from pulling out more than a gallon or two. A particularly strong pumpout can even implode a tank.
When air displaced by incoming waste cannot escape out the vent the tank becomes pressurized, creating increasing back pressure that prevents the toilet from flushing.
So...Do NOT use the toilet again or try to pump out or dump the tank until you've cleared the vent. Without a source of air to replace contents as they're being sucked out of the tank, the pump will pull a vacuum that'll prevent it from pulling out more than a gallon or two. A particularly strong pumpout can even implode a tank.
The two most common locations for a vent blockage are the vent thru-hull and the other end of the vent line--that end of the hose and the vent fitting on the tank. Start by cleaning out the thru-hull...use a screwdriver blade, ice pick--whatever works. If the thru-hull is one that has a screen in it, knock it out...screens cause more problems than they prevent. If that doesn't result in a spew out the vent, you'll need to relieve the pressure before removing the vent line from the tank to clean them out...so open the deck pumpout fitting VERY CAREFULLY with a hose at the ready. Be sure you're UPwind of it! Scrape out that end of the vent line and the vent fitting on the tank...reconnect the vent line.
If there's a filter in the vent line, remove it...once a filter gets wet--which can happen when a tank is overfilled or even due to heeling--the charcoal swells and blocks the vent...one of the reasons why vent filters aren't recommended for use on most sailboats.
I also recommend that you replace the "vent" thru-hull--which is designed to keep sea water out of the fuel and water tanks, but boat builders use 'em on holding tanks too--with an open bulkhead or "mushroom" thru-hull that'll prevent vent blockages by letting you put a hose nozzle against it to backflush the vent line every time you wash the boat and/or pumpout.
--Peggie