Herein, optimized headspace solid phase microextraction with gas chromatography–tandem mass spectrometry (HS-SPME-GC-MS/MS) was used to estimate the 2-acetyl-1-pyrroline (2-AP) in raw and cooked rice samples of ten different traditional and improved varieties. Furthermore, HS-SPME-GC-MS-based volatile profiling was subjected to untargeted analyses to identify major odorants in raw and cooked rice samples, and to understand chemical proximities among volatile profiles. Results showed that 2-AP content was remarkably increased in cooked rice compared to raw. Among the varieties studied, Pusa-1652 (Improved Kala Namak) and Kala Namak-2 were superior in the 2-AP content than Basmati varieties. Additionally, Govind Bhog, Kala Jeera and Jeera-32 had 2-AP content equivalent to or superior to Basmati rice varieties. Altogether, 18 and 22 volatiles were identified in the raw and cooked rice samples studied, respectively. Of these, ethyl butyrate, ethyl 3-methylbutanoate, 2-undecanone, ethyl benzoate, ethyl benzeneacetate, 2-methylnaphthalene, and 1-methylnaphthalene were characteristically detected in the cooked rice. The high amount of 2-ethyl-1-hexanol was uniquely found in raw rice samples, which can be a marker compound for freshly milled rice. Along with 2-AP, butanoic acid and benzoic acid derivatives, phenylethyl alcohol, ethyl 3-hydroxybutyrate, and indole may be responsible for the overall perceived characteristic Basmati-like aroma in cooked rice.