The value hotel chain scored 83 per cent in this year's report, with five stars awarded in every category except for value for money.
Radisson Blu Edwardian also scored highly (75 per cent) joining Premier Inn as a Which? Recommended Provider.
Of the 26 hotel chains considered in the large hotel chain category (for hotels with 21 or more properties in the group, worldwide), the 51-strong Britannia hotel chain received the lowest score (39 per cent), receiving just one out of five stars for the quality of its bathrooms and bedrooms and for its description matching the reality.
Premier Inn managing director Simon Jones, said the company was delighted with the findings.
"To have scored top marks across so many of the measures is testament to all of our team across our whole business," he said.
“Being recommended by Which? is fantastic, not only as recognition for our teams, but it confirms what our existing customers already know and what we hope potential customers will soon come to discover.”
Small hotel chains
Malmaison received the highest customer score in the small hotel chain category. The 13-strong group scored 77 per cent, narrowly beating Hastings Hotels and its sister brand Hotel du Vin, who both received scores of 75 per cent.
Pub operator and brewer Young's received the lowest score of 55 per cent for its hotels in the small hotel chains category, which could only include companies with under 20 properties.
To compile the annual report, Which? asked its members and the general public in the summer to complete an online survey about their experience staying in small and large hotel chains in the last year.
The large hotel chain results are based on 5,991 Which? member experiences while the small hotel chain results are based on 323 general public experiences.