After graduating from university, Lin returned to Taiwan. She intended to pursue a career in fine art and sought a position at the Taipei Fine Arts Museum, but was turned away because she lacked a postgraduate degree in the field. Lin continued to model part-time before leaving the industry and working as an administrative assistant for the Fubon Cultural and Educational Foundation. In 2000, Lin left Fubon and spent three months studying in Japan, then returned to Taiwan and modeling, with Catwalk Production House.

In 2002, Lin was invited to model in a television advertisement in Hong Kong. The advertisement received attention and discussion on the internet, and interest in Lin began to grow. The following year, noted television producer Ge Hongfu offered Lin a position as hostess of a fashion program on Shanghai Oriental Television. In 2004, Lin starred in a broad series of advertisements in Taiwan that included big giant building-size posters, billboards, and television commercials. Almost overnight, Lin skyrocketed to national fame and became an instant celebrity model. Her rise to fame initiated a Taiwanese craze for supermodels, an effect commentators named “The Lin Chi-ling Phenomenon” (Chinese: 林志玲現象; pinyin: Lín Zhìlínɡ xiànxiànɡ).

Lin’s popularity grew throughout the rest of 2004, as she began modeling in Hong Kong and Mainland Chinese advertisements, and continued when she began doing Japanese advertisements in 2005. From 2004 to 2006, Lin served as Taiwan’s goodwill ambassador to the Japan Tourism Association. One of the unintended results of Lin Chi-ling phenomenon is that due to Lin’s popularity among her Chinese fans, some Japanese pornographic actresses resembling Lin have become more famous and more popular among Chinese fans than their native homeland Japan, and received nicknames given by their China fans in association with Lin Chi-ling, such as in the case of Yui Hatano, who is frequently referred by Chinese fans as AV Lin Chi-ling, and Nozomi Aso (麻生希/あそう のぞみ), who is frequently referred by Chinese fans as AV little Lin Chin-ling. On 8 August 2005, Lin was in Dalian, China, shooting an advertisement for Procter & Gamble home products when she fell from the back of a horse she was riding and was inadvertently trampled. Workers rushed Lin to a nearby hospital where doctors discovered that she had suffered six broken ribs, a punctured left lung, and an accumulation of blood in the pleural cavity. Lin underwent four months of treatment and therapy, and announced in November 2005 that she had completely recovered.

Lin has had numerous roles in television over her time as a model, being the host of TVBS-G LA Mode News, TVBS-G Fashion Track, the Golden Melody Awards and the Top Chinese Music Chart Awards in 2005.

As of 2006, Lin has served as an official spokesperson for both China Airlines and Longines.

Taiwanese media reported Lin as #1 model in the “Richest Celebrities [in Taiwan]” list in 2007, with estimated earnings of NT$60,000,000 (≈ AU$2,100,000 ≈ CA$1,900,000 ≈ UK£906,000 ≈ US$1,900,000), in which Jay Chou appeared as #1 male singer (with over NT$100,000,000) and Jolin Tsai appeared as #1 female singer (with nearly NT$100,000,000).

Lin has made her film début role in a historical epic directed by John Woo entitled Red Cliff. Playing the role of Xiaoqiao, it was her first time acting. In 2009, she starred together with Jay Chou in the action-adventure film The Treasure Hunter.

Lin starred as one of the three female leads in the 2010 Fuji TV Japanese television drama Tsuki no Koibito. The male lead is a popular actor Takuya Kimura.

Hong Kong press reported she was 2009’s #1 highest-paid model in the Greater China region, followed by Chinese Jennifer Du (#2), Hong Kong’s Gaile Lai (#3) and Lynn Hung (#4). She has continuously ranked #1 on Taiwan’s “Highest-earning models” list since 2004. Her earnings was estimated to be NT$160,000,000 (≈ AU$5,400,000 ≈ CA$5,400,000 ≈ UK£3,370,000 ≈ US$5,320,000) in 2010, which consisted of those from advertisements (NT$120,000,000) and various such as TV-series appearance in Japan (NT$40,000,000), and NT$200,000,000 (≈ AU$6,600,000 ≈ CA$6,800,000 ≈ UK£4,240,000 ≈ US$6,600,000) in 2011.

Lin was in an on and off relationship with Taiwanese actor Jerry Yan for many years. Yan admitted to reuniting with Lin on 10 November 2017, but this was neither confirmed nor denied by Lin. Around one year later, however, Yan refused to comment and Lin denied dating. On 6 June 2019, Lin announced her marriage to Akira, a member of the Japanese pop band Exile.