As an astrophysicist, I am content with the current roster: it includes Arved-Ervin Sapar, a theoretical astrophysicist; Jaan Einasto, famous for his work on the large-scale structure of the Universe; and Ene Ergma, known for her work on compact objects and gamma-ray bursts. Notably, academic Ergma is currently serving her second term as Speaker of the Riigikogu (the Estonian parliament), and was a visiting professor at my current academic home, the Anton Pannekoek Astronomical Institute.
Other notable academics include the physicist and former Rector of the University of Tartu Jaak Aaviksoo, currently Minister of Defence (sic!), and Jüri Engelbrecht, currently president of ALLEA, the European Federation of National Academies of Sciences and Humanities.
References:
[1] News report in Eesti Päevaleht OnLine (in Estonian), http://www.epl.ee/artikkel/416462
[2] Estonian Academy of Sciences website