Powder-bed beam-based metal additive manufacturing (AM) such as electron beam additive manufacturing (EBAM) has a potential to offer innovative solutions to many challenges and difficulties faced in the manufacturing industry. However, the complex process physics of EBAM has not been fully understood, nor has process metrology such as temperatures been thoroughly studied, hindering part quality consistency, efficient process development and process optimizations, etc., for effective EBAM usage. In this study, numerical and experimental approaches were combined to research the process temperatures and other thermal characteristics in EBAM using Ti–6Al–4V powder. The objective of this study was to develop a comprehensive thermal model, using a finite element (FE) method, to predict temperature distributions and history in the EBAM process. On the other hand, a near infrared (NIR) thermal imager, with a spectral range of 0.78 μm–1.08 μm, was employed to acquire build surface temperatures in EBAM, with subsequent data processing for temperature profile and melt pool size analysis. The major results are summarized as follows. The thermal conductivity of Ti–6Al–4V powder is porosity dependent and is one of critical factors for temperature predictions. The measured thermal conductivity of preheated powder (of 50% porosity) is 2.44 W/m K versus 10.17 W/m K for solid Ti–6Al–4V at 750 °C. For temperature measurements in EBAM by NIR thermography, a method was developed to compensate temperature profiles due to transmission loss and unknown emissivity of liquid Ti–6Al–4V. At a beam speed of about 680 mm/s, a beam current of about 7.0 mA and a diameter of 0.55 mm, the peak process temperature is on the order around 2700 °C, and the melt pools have dimensions of about 2.94 mm, 1.09 mm, and 0.12 mm, in length, width, and depth, respectively. In general, the simulations are in reasonable agreement with the experimental results with an average error of 32% for the melt pool sizes. From the simulations, the powder porosity is found critical to the thermal characteristics in EBAM. Increasing the powder porosity will elevate the peak process temperature and increase the melt pool size.