Solana collected the accolade in the southwestern Polish city of Wrocław on Saturday, state news agency PAP reported.
Wrocław Mayor Jacek Sutryk said during the ceremony that Solana "played a key role in the process of bringing Poland into the alliance."
He added that Solana's "constant commitment and visionary approach provided Poland with not only security, but strong support from allies in the face of modern threats.”
Solana held the reins of the alliance when it expanded to admit Poland, the Czech Republic and Hungary in 1999.
He said in an acceptance speech that "opening NATO to new members, especially Poland," had been his "obsession" at the time.
He added that Poland was eager to embrace NATO's values of freedom, democracy and the rule of law and showed its determination to become a member of the Western alliance after decades under Soviet control.
Photos: PAP/Maciej Kulczyński
"I was proud that Poland joined NATO when I was secretary-general," Solana told those at the ceremony.
Solana served as NATO chief from 1995 to 1999. He was one of the architects of Poland’s NATO entry on March 12, 1999, according to officials.
The Jan Nowak-Jeziorański Award, presented annually in Wrocław, the capital of Poland's southwestern Lower Silesia region, was established in 2004 by local authorities and institutions including the University of Wrocław, the Ossolineum National Institute and the College of Eastern Europe.
The honour is awarded to individuals who "embody thinking about the state as a common good," as well as to institutions that "made a significant contribution to the overthrow of communism, Poland regaining independence, and to the shaping of civil society in the countries of Central and Eastern Europe."
The award is named in honour of Jan Nowak-Jeziorański (1914-2005), a World War II hero who spent his life fighting for an independent Poland and headed the Polish section of Radio Free Europe for over two decades during the Cold War era.
Nowak-Jeziorański during the war served as a courier for Poland's underground Home Army (AK), smuggling information to London, where the Polish government-in-exile was based.
He took part in the 1944 Warsaw Uprising against the Polish capital's Nazi German occupiers.
He ultimately escaped to the West, running the Polish section of Radio Free Europe from 1952 to 1976.
In 1996, Nowak-Jeziorański was awarded America’s highest civilian award, the Presidential Medal of Freedom, by then-President Bill Clinton.
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Source: PAP, polskieradio.pl