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為維護君主專製、反對革命，亞歷山大采取自由主義的政策，設立所謂“非正式委員會”解决各類問題。1802年設各部大臣製。1803年頒布自由耕作法，宣告被束縛在土地上的農奴有可能得到解放。開辦哈爾科夫大學和喀山大學。
對外政策方面，參加第三、第四次反法同盟，在奧斯特裏茨、弗裏德蘭的會戰中失敗。1807年與拿破侖簽訂提爾西特和約。之後得到法國支持，贏得了和瑞典、土耳其的戰爭，奪得芬蘭和高加索的領地。1812年擊退拿破侖對俄羅斯的遠征。1814年率領俄羅斯軍隊進擊到巴黎。不久活躍在維也納會議上，作為有力的領導人之一，結成神聖同盟。1820年左右受奧地利首相梅特涅影響，排斥歐洲的自由主義和民族主義，公然推行反動政策，加強對國內和國外自由主義力量的壓製。
性格優柔寡斷、多疑、傷感，又極其自尊自傲，被稱為“獅身人面像”。晚年沉溺於嚴重的神秘主義。
1793年娶巴登伯國的路易莎郡主(1779-1826)，俄羅斯名伊麗莎白·阿列剋謝耶芙娜。有兩個女兒，但皆早夭。
He was born in Saint Petersburg to Grand Duke Paul Petrovich, later Emperor Paul I, and Maria Feodorovna, daughter of the Duke of Württemberg. Alexander was the eldest of four brothers. He succeeded to the throne after his father was murdered, and ruled Russia during the chaotic period of the Napoleonic Wars. In the first half of his reign Alexander tried to introduce liberal reforms, while in the second half he turned to a much more arbitrary manner of conduct, which led to the revoking of many early reforms. In foreign policy Alexander gained certain successes, mainly by winning several military campaigns. In particular under his rule Russia acquired Finland and part of Poland. The strange contradictions of his character make Alexander one of the most interesting Tsars. Adding to this, his death was shrouded in mystery, and the location of his body remains unknown.