Study has been made of the thermoluminescence yield of various novel tailor-made silica fibres, 6 and 8 mol % Ge-doped, with four differing outer dimensions, comprised of flat and cylindrical shapes, subjected to electron irradiation. Main thermoluminescence dosimetric characteristics have been investigated, including the glow curve, dose response, energy dependence, minimum detectable dose, effective atomic number, linearity of index and sensitivity of the fibres. The studies have also established the uncertainties involved as well as the stability of response in terms of fading effect, reproducibility and annealing. In addition, dose-rate dependence was accounted for as this has the potential to be a significant factor in radiotherapy applications. The 6 and 8 mol % fibres have been found to provide highly linear dose response within the range 1 to 4 Gy, the smallest size flat fibre, 6 mol% Ge-doped, showing the greatest response by a factor of 1.1 with respect to the highly popular LiF phosphor-based medium TLD100. All of the fibres also showed excellent reproducibility with a standard deviation of < 2% and < 4% for 6 and 8 mol % Ge-doped fibres respectively. For fading evaluation, the smallest 6 mol% Ge-doped dimension flat fibre, i.e., 85 × 270 μm displayed the lowest signal loss within 120 days post-irradiation, at around 26.9% also showing a response superior to that of all of the other fibres. Moreover, all the fibres and TLD-100 chips showed independence with respect to electron irradiation energy and dose-rate. Compared with the 8 mol% Ge-doped optical fibres, the 6 mol% Ge-doped flat optical fibres have been demonstrated to possess more desirable performance features for passive dosimetry, serving as a suitable alternative to TLD-100 for medical irradiation treatment applications.