|Statue of Anna in Senlis, France|
His years-long search for a new bride over, Henry and Anna married on 19 May 1051, in Reims Cathedral. A year later, she bore Henry a son, Philip I. "Philip" was not a common name in France prior to this; it may be that the Greek name was introduced by Anna: the area around Kiev was identified with Scythia, which was supposedly converted to Christianity by St. Philip, making his name important to that culture.
The political alliance formed by this marriage was fortunate for France: it gave them links to important families in Byzantium and Sweden; it gave them an ally in Kiev on the far side of France's potential rival, the Holy Roman Empire. But the transition from Kiev to France could not have been easy for Anna. In a letter to her father, she says France is "a barbarous country where the houses are gloomy, the churches ugly and the customs revolting."
Anna was accustomed to a very different society. She knew five languages, including Greek and Latin, and considered the majority of Franks illiterate—including her new husband, who signed his name with an "X". She was also used to fancier dining: her wedding feast had only three courses, whereas at home she was accustomed to five courses at dinner.
When Henry died in 1060, she continued to show her intellect by acting as regent for young Philip and impressing many with her political acumen, including Pope Nicholas II, who wrote a very friendly letter to her, praising her for her wisdom and piety.
That piety and wisdom did not prevent her from the emotional act of falling for Count Ralph III of Valois, who decided to marry Anna in 1062. Unfortunately, this upset Count Ralph's wife, who felt that being told "I don't want you any more" was not sufficient as a divorce proceeding. She appealed to Pope Alexander II, who declared Ralph an adulterer and excommunicated the couple. Ralph, who would not return to his former wife, died in 1074. Anna returned to court, forgiven by her son. She died a year later.