While a simple "Hi," "Hello," or even "Hey" is appropriate in casual correspondence, a more formal salutation is appropriate when you are emailing about a business_related matter, such as a cover letter, letter of recommendation, or inquiry letter.
Business writing varies from the conversational style often found in email messages to the more formal, legalistic style found in contracts. A style between these two extremes is appropriate for the majority of memos, emails, and letters. Writing that is too formal can alienate readers, and an attempt to be overly casual may come across as insincere or unprofessional. In business writing, as in all writing, you must know your audience.