I think it is a very effective method when approaching smaller businesses, small chains or franchises. However, larger companies tend to manage their recruitment process solely online now. I’d always recommend finding out if this is the case. Printing isn’t cheap and there is no point wasting your time. Boots, for example, can’t do anything if you send them a CV, you have to go online to apply for vacancies if there are any at the time,
Put it in an envelope is definitely a good idea, and try and engage the manager for a minute or two just so they know who you are. Be polite, listen to them, don’t overpower them, and keep it short and sweet. Make sure you look smart too. Scruffy tracksuits and dirty shoes with crow’s nest hair can say a lot about you and your attitude.