May 1903 Urusov was appointed Governor of Bessarabia, whereafter he immediately purchased a guidebook of the area; he would go on to confess that he knew virtually nothing of the area, saying he 'knew as little of it as I did of New Zealand, or even less.' Despite viewing the appointment to this position in a distant corner of the Empire as a form of exile, he set off, after a short briefing with the Tsar in St. Petersburg, three weeks later by train to Bessarabian capital Kishinev from Moscow. The journey took two nights and three days, which Sergey spent in his private compartment studying his purchased guidebook to prepare himself for the meeting with the civic dignitaries, whom he expected to meet at arrival. Despite writing to his Vice-Governor requesting he keep the reception party small, Urusov was met by a crowd of people and an orchestral band at Bendery, the first major Bessarabian town; with a group of policemen cordoning off the Vice-Governor in a complete dress uniform, alongside the city mayor with a platter of bread and salt, Urusov was greeted as Governors had traditionally been greeted in Bessarabia. One and a half hour later Urusov arrived at the administrative centre of Bessarabia: Kishinev; here he was driven round the city in an open carriage, with the sidewalks packed with bystanders who 'bowed, waved their handkerchiefs', with some even going down on their knees. A modest man, he admitted to being 'struck' by the matter, as he was not familiar with such displays of reverence. After a blessing in the Kishinev cathedral he arrived at the Governor's Residence, a palace in neo-classical style in the city centre. Impressed by the city centre's architecture, its paved boulevard and streets lined with white acacias and poplars, large stone buildings, he noted that it would 'have made no unfavourable impressing' even in the Empire's capital St. Petersburg. As a local celebrity, he was refused to travel except in a carriage with the Chief of Police and a mounted guard escort. The provincial society was alien to him and he was taken back by the 'god-like esteem' he was held in, as well as the local aristocratic customs.
, who was given the task of assembling the first cabinet government in October offered 'the liberals' several important positions: Sergey Urusov was offered the important post Minister of the Interior; he was soon rejected though on the grounds that 'he was not a commanding personality', although 'decent' and 'fairly intelligent'. The post went to Pyotr Durnovo, a lawyer and statesman with a somewhat scandalous past and poor record, who apparently had been promised the position.
