Voivodeship's capital, the biggest and its most important city was Lwów. It consisted of 27 powiats, 58 towns and 252 villages. In 1921 it was inhabited by 2,789,000 people. Ten years later, this number rose to 3,126,300. In 1931, the population density was 110 per km². The majority of the population was Polish, especially in western counties. Ukrainians made up about 33% and Jews - around 7%. Also, there were smaller communities of Armenians, Germans and other nationalities. In 1931, the illiteracy rate of the Voivodeship's population was 23.1%, about the same as national average and, at the same time, the lowest in the Polish Eastern Borderlands.
Lwów, the voivodeship's capital, was by far its biggest city, with the population of 318,000. It was also the biggest city in south-eastern Poland and the third biggest city in the country, before Kraków. Other important centers in the voivodeship were: Przemyśl, Borysław, Drohobycz, Rzeszów, Jarosław, Sambor, Sanok and Gródek Jagielloński.
Interwar Poland was unofficially divided into two parts - Poland "A" and Poland "B". Lwów Voivodeship was located on the boundary line of these, with two main centres - the city of Lwów itself and the rich in oil southern region of Borysław and Drohobycz. Starting in the mid-1930s, the Polish government decided to start a massive public works project, known as Centralny Okreg Przemyslowy. The project covered western counties of the Voivodeship, where several factories were constructed. This was a huge boost for overpopulated rural areas, where unemployment was high. The project was still incomplete at the beginning of the Second World War. The railroad network was well-developed only in the area of Lwów, as the city itself was an important hub with as many as eight lines coming from it. Apart from this, some counties lacked rail connections, while others were greatly underdeveloped. Other rail hubs were Rawa Ruska, Rzeszów, Rozwadów, Sambor, Drohobycz, Przeworsk, Chodorów, and Przemyśl. As for January 1, 1938, total length of railroads within Voivodeship's boundaries was 1,534 kilometers, which was 5.4 km. per 100 km².
Following the Molotov–Ribbentrop Pact and the subsequent Russo-German conquest of Poland, the voivodeship was divided by the victors in late September 1939. The western part of the voivodeship was annexed by Germany and added to the General Government, while the eastern part was incorporated into the Ukrainian Soviet Socialist Republic. After July 1941, Lwów and the eastern part were occupied by Germany and also added to the General Government; the Polish underground administration existed there until August 1944. In 1945, when Poland's current borders were established, the western part of former Lwów Voivodeship was organized into the newly created Rzeszów Voivodeship; this territory has been part of the Subcarpathian Voivodeship since 1999. The remaining eastern part became Ukraine's Lviv Oblast.
