Yes! You just need to set up a new shipping class for only the country you are based in. Call the class something obvious (such as 'Local Pickup' or 'Collection Only') and set the price to $0.00.
Be aware that any customer with a shipping address in your country will have this as the default shipping option and will need to manually select the higher-priced option if they can't collect their order. Occasionally customers don't notice this and checkout without paying for shipping. However it is easy enough to send a quick email to the customer, explaining the situation, and to send a PayPal invoice for the shipping cost.