This paper is focused on an overview of developments and validation procedures in analytical methods for the detection and quantification of emerging contaminants from multiple groups of environmental contaminants in the environment: polyaromatic hydrocarbons (PAHs), phthalate esters (PEs), alkylphenol ethoxylates (APEOs), alkylphenols (APs), and butylated hydroxytoluene (BHT) in river sediments. Especially, the simultaneous extraction of several analyte groups from sediment samples is currently uncommon, but from the perspective of green analytical chemistry, it is highly desirable. In simultaneous analysis, multiple groups of substances are determined at once instead of through several individual analyses, saving energy, time, and chemicals while significantly increasing laboratory throughput. This review reports different approaches for monitoring the presence of environmental contaminants from four different groups of contaminants from river sediments. There are plenty of sampling techniques, with the core and grab sampling being the most employed at present. Sample preparation is a challenging part of the whole analytical method, providing ample opportunity for optimization in accordance with green analytical chemistry principles. Various extraction schemes, including ultrasound-assisted extraction techniques, accelerated solvent extraction, and microwave-assisted extraction are energy-intensive techniques but may be considered "green" due to their possibility to reduce the consumption of organic solvents, which are usually considered toxic. Quick, Easy, Cheap, Effective, Rugged and Safe extraction (QuEChERS) in the case of satisfactory validation parameters is well-evaluated and utilized. The most recent developments in extraction and clean-up techniques for simultaneous analysis of two, three or four groups of contaminants are showing promising results. Separation and detection techniques are shortly discussed. Further optimizations of analytical methodologies are needed, and future developments in the field of analytical methods for sediment samples are expected for more efficient and faster acquisition of data on the presence of contaminants in real monitoring samples.