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 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 TWD$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 TWD$100,000,000) and Jolin Tsai appeared as #1 female singer (with nearly TWD$100,000,000).

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 TWD$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 (TWD$120,000,000) and various such as TV-series appearance in Japan (TWD$40,000,000), and TWD$200,000,000 (≈ AU$6,600,000 ≈ CA$6,800,000 ≈ UK£4,240,000 ≈ US$6,600,000) in 2011.

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