The LaTeX command for equiv (≡) is \equiv (identical to / congruent).
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Write \equiv inside math mode, that is between $…$ for inline math or in a \[ … \] or equation block for display math. It is part of core LaTeX math, so no extra package is required.
As a relation, \equiv gets a thick space on each side, and a long inline formula may break after it. With unicode-math under XeLaTeX or LuaLaTeX, typing ≡ in a formula gives the same symbol.
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Use \equiv in math mode; it needs no extra package. For example, $a \equiv b$.
None: \equiv is built into LaTeX, so no extra package is required.