A large number of uniformed police officers were seen clashing with the supporters down High Street Kensington, in the hours ahead of the Group C match.
Bystanders saw a number of supporters throwing punches at the police, who responded by kettling the travelling fans and escorting them down the road towards Earls Court.
Around 10 police vans arrived to quell the disruption, which briefly brought the busy road to a standstill during rush-hour.
The Metropolitan Police confirmed to The Independent that one arrest had been made after the incident, which took place shortly before 6.00pm.
Away tickets for tonight’s European match, which kicks off at 7.45pm at Stamford Bridge in south-west London, sold out long in advance of the fixture, with both sides needing to win to keep their campaigns on track.
This is not the first time that Roma’s supporters have found themselves at the centre of controversy this week, as on Tuesday the club were fined €20,000 for offensive anti-Neapolitan chants, as well as a further €10,000 for throwing a flare.
The two sides met on Saturday night, with Napoli taking a 1-0 win at the Stadio Olimpico.