In the last decades, materials characterisation techniques have been employed in assessment of various types of newly-developed concretes such as geopolymer concrete, recycled and by-product concretes and fibre and nanofibre concretes. Characterisation have been also used to understand durability issues resulted from exposure of concrete structures to harsh and corrosive agents such as maritime environments and concrete members in acid sulphate soils. These corrosive environments can deteriorate and degrade concrete components and lead to loss of integrity of concrete and diminishing the structural performance and serviceability. The use of microstructural analysis in assessing concrete performance such as resistance to fire and the flexural strength, can also be of assistance to improve these properties of concrete. Some of these characterisation methods include scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray mapping (XRM), X-ray diffraction (XRD), simultaneous thermal analysis (STA), thermal mechanical analysis (TMA) and Fourier-transform infrared spectroscopy (FTIR). Although the mentioned methods are well-stablished techniques, firstly, there is a big gap between the experts who can appropriately use them and the structural/materials engineers. Secondly, despite all the benefits they possess, their complexity seems to cause an obstacle for engineers to use them in practice. This paper discusses the application of characterisation techniques through simple examples for engineering practices in concrete structures and the useful outcome these analyses provide to engineers, focusing on the necessity of sufficient knowledge when application and sample preparation.