Blockchain technology represents a revolutionary approach to tracking and storing business transactions and data in a transparent, immutable, and distributed way. The goal of this research is twofold. It presents the proposal of a new e-government business model based on blockchain and examines the possibilities of citizens’ readiness to use new e-government services based on blockchain. Introducing blockchain technology in e-government business can contribute to reducing administrative barriers, faster exchange of data, and increased trust among different participants. For the technology to be implemented and sustainable, it must be willingly accepted by government, businesses, and citizens. To examine the citizens’ readiness to use e-government services based on blockchain technology, research was conducted using the UTAUT2 model with extended perceived risk and trust. It was found that the greatest importance of the expected behavior is trust, performance expectancy, facilitating conditions, and habit among young citizens.