I love Ursula K Le Guin and have been slowly going through the so called Hainish cycle novels and stories. It can be an intimidating series to get into because it's not a linear story, the works are set in a so called Ekumen of planets but each novel is written in a differnt time period with differnt characters, and it was never intended to be a series so sometimes different texts will adress things in opposite ways.
Ursula has shared a supposed reading order when the tittles were release as a collection, you can find it here https://www.ursulakleguin.com/hainish-novels-and-stories?rq=the%20hainish%20cycle She herself seems to not take the idea of a specific reading order very seriously, and I wouldn't take anything to heart.
Personally I would start with the works already set in a time when the Ekumen exist, they are the most famous novels, and were written a little later so I do find their ability to adresss different political aspects more developed and interesting. The short story "The word for world is forest" is a great starting point since it's a very quick read and you can already get into ursula's narrative style and her intelligent approach to social issues. Then I would do to either The Dispossed or The Left Hand of Darkness, the one that grabs your interest really.
I would also recommend "The Wind's Twelve Quarters", a collection of short stories, though most are not sci-fi per say, it features the famous The one who walk away from Omelas", and the prologue to the hainish cycle "Semley's Necklace" (that is usually featured along some publications of Rocannon's World).
Anyways, I hope you can get into her work, it really is incredible. And if you would like short silly reads I would send you to The Annals of Pard, a diary she had on her blog where she writes the adventures between her and her cat Pard https://www.ursulakleguin.com/blog/42-choosing-a-cat