Short films by Stephen Frears, the late John Schlesinger and brothers Tony and Ridley Scott can now be downloaded from the British Film Institute's website.
Schlesinger's 1961 short Terminus is set in London's Waterloo station
The initiative allows users to watch rarely shown early works from some of Britain's leading film-makers.
Six features are also available, among them 1974's Pressure - regarded as one of Britain's first black feature films.
There are 230,000 films and 675,000 TV programmes in the BFI archive. Download costs range from £5 to £12.50.
Film minister Shaun Woodward said the scheme ensured that "vintage and rarely-seen films are now no longer the preserve of the arthouse cinema-goer".
"This is a fantastic resource for the public who will now, more easily, get to see films from a bygone era."
There are 21 downloads available in the first wave of content, with new additions to follow each month.
Rarities include South, a 1919 silent documentary about Sir Ernest Shackleton's expedition to Antarctica; Michael Powell's 1937 film The Edge of the World; and more recent works featuring Doctor Who actors David Tennant and Christopher Eccleston.
"Film and television are a social record, a historical resource [and] a chance to travel through time," said BFI director Amanda Nevill.
"We are well on the way to meeting the challenge of opening up this extraordinary resource even more."