Sydney 'Syd' Woolfe first appeared in Emmerdale in March 2002, as a builder working alongside Jerry 'Mack' Mackinley. Upon his arrival, Syd caught the eyes of many female residents due to his good looks and his charming nature. Syd moved in with local mechanic Scott Windsor and his girlfriend Chloe Atkinson. After Mack left the village Syd remained there to continue work. He became best friends with Scott, but found himself attracted to Chloe. However, initially he didn't let his heart rule his head and decided to keep his feelings to himself, in the meantime enjoying flings with Angie Reynolds and Nicola Blackstock.
However Syd found it increasingly difficult to keep his feelings to himself and eventually he and Chloe began sleeping together. While they were having sex one day while Chloe was looking after baby Jean Tate, Jean fell from her car seat and Chloe and Syd covered up any signs of an accident. However Jean's mother Zoe Tate noticed that Jean was crying repeatedly and took her to hospital where she found that Jean had broken ribs. Syd, feeling guilty, revealed what had happened, leading to Scott eventually finding out about their affair leading to several fights between him and Syd. Eventually Syd moved out of Scott's house and moved in with Chas Dingle, but continued his affair with Chloe. However, Chloe didn't take the relationship as seriously as Syd and the pair ended up having a number of arguments over this, before Chloe eventually left Syd, who then reconciled his friendship with Scott.
Syd continued his escapades when he went to a lap dancing club with Scott and Robert Sugden. During his time there he seduced and had sex with lap dancer Yolanda. When Chloe found out about this she was instantly jealous, and when Syd realized this he constantly wound her up about it. Syd was also happy to let Danny Daggert and Katie Sugden move in with him and Chas.
Syd and Chas' friendship remained strong but Syd found himself falling for her and he took her away on holiday for a couple of nights, although nothing transpired. Syd was left feeling down when Chas began a relationship with newcomer Carl King, and once again chose to keep his feelings to himself, in the meantime anyway. One night Syd, Danny, Robert Sugden and Paul Marsden take Andy Sugden out on a stag night for his wedding to Katie but the night ends in disaster when Andy and Robert get into a fight.
Later in 2004, Scott's younger sister Donna was left traumatized when convicted rapist Frank Bernard Hartbourne approached her to help her fix her motorbike. Scott enlisted Syd's help and together they gave Frank Bernard a severe beating which left him in hospital. While Scott seemed pleased about what he'd done. Eventually the pair were found out and faced criminal charges, and Syd was shocked when Scott failed to own up to what he'd done. Syd decided to do the right thing and confessed that he had taken part in the beating of Frank Bernard. However he was let of with a police caution. Shocked at the way Scott had behaved Syd confronted him and the pair have a fallout.
Syd eventually received a job offer in Manchester, but was left contemplating whether to take it or not. He was struggling whether to tell Chas, one of his closest friends, how he really feels about her. Eventually after they both start drinking together Syd tells her how he feels and tries to make a pass at her. However Chas gently knocks him back and subsequently Syd decides to take the job in Manchester. Before leaving he bids farewell to Edna Birch and while walking past Scott he spits on his shoes in response to Scott's behavior. Syd then says a tearful farewell to Chas before leaving in his van for Manchester.