Man and Superman, National Theatre, review: Ralph Fiennes gives one of the best performances of his career

You don't necessarily expect to be treated to the distinctive tones of Kirsty Young at the start of a marathon Shaw revival. Simon Godwin's remarkably assured and effervescent modern-dress production of Man and Superman kicks off, though, with a cheeky but pertinent Desert Island Discs gag. We hear Young introducing, as her castaway, the “provocateur” protagonist and author of a handbook designed to “set a new direction” for society, whom we are about to meet – and his first choice of record is the overture to Mozart's Don Giovanni which swells forth.

This sets the tone for a piece, which Shaw fittingly subtitled “a comedy and a philosophy”, in which the Don Juan myth is updated, with the roles pointedly reversed. The libertine has now turned revolutionary ideologue, his defiance of convention expressed through a determined flight from sexual relations with women who are seen as biologically driven by the “Life Force” to entrap men into marrying and impregnating them. The true “philosophic man”, by contrast, is bent on discovering the “inner will” of this force in its ever-higher forms of organization and self-consciousness. (The production makes a piquant pairing with The Hard Problem, Tom Stoppard's neuroscience play, at the Dorfman next door.)

Man and Superman doesn't often get an outing – it was last staged at the NT in 1981 with Daniel Massey – and it's not hard to see why. But Godwin has edited down its daunting length to a very manageable three hours, while rightly retaining the normally cut dream sequence in the third act which is both the dialectical core of piece and influences the outcome of the romantic comedy that flanks it. And Ralph Fiennes gives one of the best performances of his career as Jack Tanner, the rich rebel who is pursued from London through the wilds Sierra Nevada, on a detour to Hell and back, and finally to Granada by Ann Whitefield, his ward, implacable would-be mate and in every way his match in Indira Varma's wittily mettlesome and spiky portrayal.

Tanner's loquacity is so pronounced that it becomes a running gag and could have you lurching for the ear-plugs. But Fiennes in his charismatic, very intriguing account of the character – a bearded figure who here seems stiff and ill-at-ease in his own body – brings such a fierce, febrile energy to his cascade of (often highly contentious) contrarian paradoxes that you begin to wonder whether Tanner's untiring, not to say, tiresome optimism is the willed programmatic positiveness of a temperamental pessimist. Without undercutting his message, the production emphasises those moments of comic deflation when it turns out that this visionary has failed to notice the glaringly obvious and the droll sheepishness with which he eventually capitulates to Anne in a Beatrice-and-Benedick-style resolution. The hectoring is humanised.

The cast are superlative with Tim McMullan excelling as a cool-cat, skinny-jeaned Devil, mellifluously almost getting the better of the argument in hell, and as a woebegone Spanish brigand whose solemn recital of his preposterous, love-lorn verses is blissfully funny. Keenly recommended.

To 17 May; 020 7452 3000; NT Live broadcast on 14 May (www.ntlive.com)