Arundell's five tries put England on verge of World Cup quarters
Arundell's contributions helped the 2003 winners move clear at the top of Pool D and a victory over Samoa on October 7th would secure their spot in the knock-out phase.
Captain Owen Farrell, back after suspension, moved to within one point of Jonny Wilkinson's England points-scoring record.
Chile lost a third straight match, conceding 11 tries, in their first appearance at a World Cup.
England head coach Steve Borthwick made wholesale changes from last weekend's victory over Japan as Marcus Smith started a Test at full-back for the first time.
Chile coach Pablo Lemoine also rotated his outfit as his side, known as Los Condores, played England for the first time in their history.
Smith showed his ability with ball in hand after just six minutes, his goose-step and grubber kick ended up with an England scrum on Chile's five-metre line but Borthwick's outfit, 16 places above the South Americans in the world rankings, failed to make the most of the chance.
England had to wait until the 20th minute to open the scoring as Chile defended superbly, with Arundell crossing in the corner after a looped Farrell pass before the skipper missed the conversion.
They doubled their advantage shortly after hooker Theo Dan pounced to score from a dominant rolling maul before Farrell this time added the extras.
The two quick tries were a blow to Chile's thin hopes of a huge upset and mistakes from Rodrigo Fernandez and Cristobal Game helped England take control of the encounter.
Despite Borthwick's conservative tactics in attack, Arundle grabbed his second after Dan turned the provider before prop Bevan Rodd secured the bonus point with five minutes of the first half to play.
Smith, 24, highlighted his quality just before the interval as he set up his try with a delicate grubber kick, which he caught with one hand.
Farrell added the conversion and England led 31-0 at the break in front of a crowd of 44,315, five thousand short of capacity at the Stade Pierre-Mauroy.
England's dominance continued after the interval as Dan scored a double and Arundell claimed his third to make it 45-0 with half an hour to play.
Borthwick brought George Ford onto the field, allowing England to have three playmakers at the same time and the move bore fruit with Arundell’s fourth try.
Ford found the Racing 92 winger out wide with a smooth assist and Arundell then collected his own chip kick for his sixth try in nine Tests with 20 minutes to play.
With 10 minutes to play, Arundell moved within one of ex-All Black Marc Ellis' record of six tries, equalling former England winger Josh Lewsey and ex-Australia full-back Chris Latham's tally.
The rout was completed as Smith and Ben Earl crossed and Farrell moved with a point of Wilkinson's England points record of 1,179 thanks to the conversion of Earl's try.
