Academically, Padmini is a graduate in Chemistry with honours from the University of Bombay, where she was a rank holder (1981). Thereafter, she completed her post-graduation in music with distinction from the SNDT University Bombay, bagging a number of honours in the process, including the Gana Hira Award for musical excellence (1984).
She is an accomplished theatre artiste and has worked in avant-garde and experimental theatre. Her skills as a polyglot are borne out by her knowledge of upto six Indian languages. Additionally, she is a holder of the Diplome de Langue Francais from the Alliance Francaise and has a working knowledge of Dutch.
She had her vocal musical initiation at a relatively tender age under the guidance of Pandit Manohar Otavkar. Thereafter, over a period of six years, she received training in the Sitar from Mrs Pramila Dagar. Discovering that her first love was for vocal music, Padmini reverted to the vocal form. She then underwent 11 years of rigorous training in voice culture under the guidance of the late Ustad Zia Mohiuddin Khan Dagar, the renowned Scholar, Dhrupad and Rudra Veena Maestro, who is a familiar name to discerning connoisseurs all over the world.
Even as her interest and musical talents flowered rapidly under the able hands of Ustad Z.M.Dagar, Padmini did her Masters Degree in Music from the SNDT University under the tutelage of Dr. Prabha Atre. This was to lay the foundation for a long and fruitful association with Dr.Prabha Atre. Her musical voyage has taken her through over two decades of hard training, polishing and perfection at the hands of these two
Besides being an accredited radio artiste, Padmini has been performing and teaching over the last 26 years. With her forte being pure classical music, Padmini remains equally at home in the light-classical forms including thumris and bhajans. She combines her love of the performing art with its academic aspects.She has participated in seminars and conducted music workshops, on music education, the practical aspects of music, music theory- like the Rasa Theory-[a theory on the aesthetic aspects of music], developmental techniques in khayal singing, music as a means for relaxation, the time-theory of music, etc. She has conducted seminars at various forums covering schools, students of music, lay audiences, music lovers and the like. She has travelled and performed extensively in various parts of the world including Asia, Europe and the USA.
As a part of her diverse musical dynamic, Padmini has been a regular visiting faculty at the Rishi Valley Education Centre and has composed the music for "Hindi Ki Duniya", an educational project of learning language through music, sponsored by Rishi Valley Education Centre and distributed through Scholastic India. She has worked with international musicians in a World Music project “Music for Life” and has composed the background score for a short film.
Padmini Rao's music is regularly broadcast on the classical music channel 'Radio Gandharva' of World Space Satelite Radio. She is an empanelled artiste of the Indian Council for Cultural Relations [ICCR] of the Government of India.