Polymer‐based pyroelectric thin films are crucial functional materials at the core of flexible and lightweight electronic devices, such as wearable monitoring sensors, energy harvesters, and infrared detectors. Nevertheless, the pyroelectric properties of the polymer films, such as poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)), vanish when the surrounding temperature exceeds the ferroelectric‐to‐paraelectric transition temperature, and thus limits their pyroelectric performance to a low‐temperature range. Herein, to mitigate this issue by employing a new class of P(VDF‐TrFE) copolymer which has a low TrFE molar content is proposed. Fine‐tuning of the structure through thermal annealing in a vacuum environment significantly favors robust and highly polarized polymer films with a large area. Electric poling combined with an optimal annealing temperature (110–120 °C) gives highly ordered ferroelectric crystalline domains in the polymer films. Consequently, this remarkably broadens the temperature range (roughly up to 140 °C) for which the polymer film still presents high pyroelectric properties (pyroelectric coefficient 50 µC (m$^2$ K)$^{−1}$). This study provides an alternative choice for pyroelectric polymer films with enhanced pyroelectricity in applications that require wider temperature ranges.