A Chronological History of Headmistresses at Diocesan Girls' School
March 1860-December 1862 Miss Wilson
  Diocesan Native Female Training School (DNFTS)
1863-1865  Miss Mary Anne Winifred Eaton  
  Diocesan Native Female Training School (DNFTS)
1866–1869 Miss Oxlad  
  Diocesan Female School(DFS)  
1867  Miss Rendle 
  Diocesan Female School(DFS)  
1899-1921 Miss Elizabeth Skipton
1921-1925 Miss Ferguson
  Miss Ferguson gave the school its motto "Daily Giving Service".
1925-1939 Miss H.D. Sawyer
  Miss Sawyer became Headmistress in 1925 on Miss Ferguson's death. The number of pupils was 222.
1939-1946 Miss E.M. Gibbins
  Miss Gibbins made the study of Chinese compulsory for all but European girls. Miss Gibbins also successfully prevented looting of the school during wartime. The war ended in 1945 and the school was re-opened on October 1st.
1946-1953 Miss A.W. Hurrell
  Though faced with such difficulties as the destruction of the school building, the absence of books and a library, Miss Hurrell was able to continue with the expansion of the existing school buildings, first with the conversion of a large dormitory from the old playshed.
1953-1985 Dr C J Symons
  In March, 1953, Dr. Symons returned as Headmistress having served twice before as Acting Headmistress. The school then numbered 644 from Kindergarten to the Upper Six. Dr. Symons had served the school for 32 years before retiring and returning to England.
1985-1999 Mrs Elim Lau
  Mrs. Elim Lau, an Old Girl of the School, took over as Headmistress from Dr. Symons in 1985.  During her term as Headmistress, she oversaw the completion of the new Building Extension Phase I in 1993 and Phase II in 1996, which allowed the Junior School to expand from 12 to 18 classes with an improved teacher-pupil ratio, and further equipped the Junior School with a new library and various special rooms for effective teaching and learning.  She retired in July 1999, having served the School for 14 years.
1999 to date Mrs Stella Lau
  Mrs. Stella Lau is also an Old Girl of the School.  She took over from Mrs. Elim Lau in September 1999. She oversaw the conversion of the Senior School from a grant school to a Direct Subsidy Scheme school and a through-train arrangement with the Junior School in 2005. She also oversaw the completion of the SIP building, the relocation of DGS to a hotel school for 2 years in Sham Shui Po while the whole school campus was redeveloped at Jordan Road between 2009-2011. The redevelopment allowed an expansion of learning facilities and departments, with a focus on learning with technology.

A Chronological History of Headmistresses at Diocesan Girls' Junior School
1975-1978 Mrs. Rachel C.A. Benton
  Prior to 1975, the Headmistress of the Senior School also acted as the Headmistress of the Junior School.  With the rebuilding of the Junior School completed in September 1975, Mrs. Rachel C.A. Benton was appointed Headmistress of the Junior School, with Dr. C.J. Symons, then Headmistress of the Senior School, remaining as Supervisor of the Junior School.  Mrs. Benton served as Headmistress of DGJS from September 1975 through August 1978.
1978-1989 Mrs Daphne Blomfield
  Mrs. Blomfield took over from Mrs. Benton in September 1978 and she remained Headmistress of DGJS until her retirement in August 1989.
1989-1999 Mrs Rebecca Yip
  Mrs. Rebecca Yip, an Old Girl of the School, succeeded Mrs. Blomfield as Headmistress of DGJS in September 1989.  She served as Headmistress for 10 years until her retirement on 11th April 1999. During her term as Headmistress, she, together with Mrs. Elim Lau, oversaw the completion of the new Building Extension Phase I in 1993 and Phase II in 1996, which allowed the Junior School to expand from 12 to 18 classes with an improved teacher-pupil ratio, and further equipped the Junior School with a new library and various special rooms for effective teaching and learning.
1999 to 2016 Mrs Emily Dai
  Mrs. Emily Dai took over from Mrs. Rebecca Yip as Headmistress of DGJS on 12th April 1999. She is also an Old Girl of the School. During her time as Headmistress, she oversaw the redevelopment of the Junior School which was completed in 2011. Mrs. Dai had served the school for 18 years before retiring in December 2016.
2017 to 2023 Mrs Annie Lee
  Mrs. Annie Lee succeeded Mrs. Emily Dai as Headmistress of DGJS in January 2017. Prior to this new position, she had served DGS for close to 20 years and was Deputy Headmistress of the Senior School.
2023 to date Dr Holly Ming
  Dr. Holly Ming took over from Mrs A. Lee in September 2023 as the headmistress of DGJS. She is an Old Girl of the School.

.