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为维护君主专制、反对革命，亚历山大采取自由主义的政策，设立所谓“非正式委员会”解决各类问题。1802年设各部大臣制。1803年颁布自由耕作法，宣告被束缚在土地上的农奴有可能得到解放。开办哈尔科夫大学和喀山大学。
对外政策方面，参加第三、第四次反法同盟，在奥斯特里茨、弗里德兰的会战中失败。1807年与拿破仑签订提尔西特和约。之后得到法国支持，赢得了和瑞典、土耳其的战争，夺得芬兰和高加索的领地。1812年击退拿破仑对俄罗斯的远征。1814年率领俄罗斯军队进击到巴黎。不久活跃在维也纳会议上，作为有力的领导人之一，结成神圣同盟。1820年左右受奥地利首相梅特涅影响，排斥欧洲的自由主义和民族主义，公然推行反动政策，加强对国内和国外自由主义力量的压制。
性格优柔寡断、多疑、伤感，又极其自尊自傲，被称为“狮身人面像”。晚年沉溺于严重的神秘主义。
1793年娶巴登伯国的路易莎郡主(1779-1826)，俄罗斯名伊丽莎白·阿列克谢耶芙娜。有两个女儿，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.